Silver phenylchalcogenate quantum dot, preparation method thereof and light-emitting device

Abstract

The invention discloses a phenyl chalcogenide silver quantum dot, a preparation method of the phenyl chalcogenide silver quantum dot and a light-emitting device. The structure of the phenyl chalcogenide silver quantum dot is as shown in a formula (I): # imgabs0 #, r is independently selected from H, D, F, Cl, Br, I, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 alkylthio group, a substituted or unsubstituted C1-C10 alkylcarbonyl group or any combination of the groups when appearing each time, and R is not all H; x is selected from S, Se or Te. The light-emitting wavelength of the silver phenylchalcogenate quantum dots ranges from 380 nm to 450 nm. The silver phenylchalcogenate quantum dot disclosed by the invention can emit blue-violet light.

Description

Technical Field

[0001] This application relates to the technical field of luminescent materials, and particularly to a silver phenylchalcogenate quantum dot, a preparation method thereof, and a light-emitting device. Background Art

[0002] Quantum dots refer to semiconductor nanocrystals with a particle size smaller than the Bohr radius of their materials, generally in the range of 1 - 10 nm. Due to the quantum confinement of electrons and holes, the continuous energy band structure becomes a discrete energy level structure with molecular characteristics and can emit fluorescence when excited. Therefore, quantum dots of different sizes can be simultaneously excited by a light source with a single wavelength. By changing the particle size of the quantum dots, their emission wavelength and Stokes shift can be adjusted. The fluorescence spectrum is narrow and symmetric, and thus quantum dots with various different fluorescence spectrum characteristics can be prepared. Quantum dots have the advantages of adjustable emission spectrum with particle size and composition, high fluorescence quantum yield, narrow emission spectrum, wide excitation spectrum, and good optical stability, and have excellent application prospects in many fields such as field-effect transistors, light-emitting diodes, photoresistors, solar cells, biological characterization, and photoelectric sensors.

[0003] High-performance long-life violet-blue quantum dots have always been the focus of research. Currently, the relatively good-performing violet-blue quantum dot light-emitting devices mainly use cadmium-containing quantum dots. However, relevant laws and regulations have strict content requirements for cadmium-containing products, and cadmium-containing products can damage the environment and harm the functions of human organs.

[0004] Silver phenylchalcogenate, for example, silver phenylselenate, is an air-stable metal-organic hybrid crystal. Similar to two-dimensional metal-organic hybrid perovskites, silver phenylselenate also has a layered structure and is a new research hotspot of non-heavy metal blue light-emitting materials, with the potential to replace traditional heavy metal quantum dots.

[0005] However, the existing silver phenylchalcogenate cannot emit blue-violet light. Summary of the Invention

[0006] In view of this, this application provides a silver phenylchalcogenate quantum dot that can emit blue-violet light.

[0007] The embodiment of this application is implemented as follows. A silver phenylchalcogenate quantum dot, the structure of the silver phenylchalcogenate quantum dot is shown in formula (I):

[0008]

[0009] Wherein, each occurrence of R independently selects from H, D, F, Cl, Br, I, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 1 -C 10 alkoxy, substituted or unsubstituted C1 -C 10 alkylthio group, substituted or unsubstituted C 1 -C 10 alkylcarbonyl group, or any combination of said groups, and not all of R are H; X is selected from S, Se or Te.

[0010] Optionally, in some embodiments of the present application, the luminescence wavelength of the silver phenylchalcogenide quantum dots is 380 - 450 nm.

[0011] Optionally, in some embodiments of the present application, the substituents of the substitution include one or more of F, Cl, Br, I; and / or

[0012] and / or, the C 1 -C 10 alkyl group is selected from methyl, ethyl, propyl, butyl;

[0013] and / or, the C 1 -C 10 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy;

[0014] and / or, the C 1 -C 10 alkylthio group is selected from methylthio, ethylthio, propylthio, butylthio;

[0015] and / or, the C 1 -C 10 alkylcarbonyl group is selected from formyl, acetyl, propionyl, butyryl.

[0016] Optionally, in some embodiments of the present application, the silver phenylchalcogenide quantum dots include AgSPh quantum dots, AgSePh quantum dots or AgTePh quantum dots; and / or

[0017] the average particle size of the silver phenylchalcogenide quantum dots is 3 - 8 nm; and / or

[0018] the fluorescence half-peak width of the silver phenylchalcogenide quantum dots is 30 - 50 nm; and / or

[0019] the fluorescence quantum yield of the silver phenylchalcogenide quantum dots is 0.1 - 3.0%

[0020] Correspondingly, the embodiments of the present application also provide a preparation method of silver phenylchalcogenide quantum dots, including the following steps:

[0021] Provide a silver precursor solution and an anion precursor, and the anion precursor includes a phenylchalcogenide compound;

[0022] Heat-treat the silver precursor solution, and then inject the anion precursor into the silver precursor solution and react to obtain silver chalcogenophenolate quantum dots;

[0023] Among them, the structure of the silver chalcogenophenolate quantum dots is shown in formula (I):

[0024]

[0025] Among them, each occurrence of R is independently selected from H, D, F, Cl, Br, I, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 1 -C 10 alkoxy, substituted or unsubstituted C 1 -C 10 alkylthio, substituted or unsubstituted C 1 -C 10 alkylcarbonyl, or any combination of the above groups, and not all of R are H; X is selected from S, Se or Te.

[0026] Optionally, in some embodiments of the present application, the silver precursor solution includes a silver precursor and a first solvent.

[0027] Optionally, in some embodiments of the present application, the silver precursor includes silver fatty acid; preferably, the silver fatty acid includes one or more of silver oleate, silver butyrate, silver n-decanoate, silver hexanoate, silver octanoate, silver dodecanoate, silver myristate, silver palmitate, silver stearate; and / or

[0028] The first solvent includes one or more of C 10 -C 30 aliphatic hydrocarbon compounds, C 10 -C 30 aromatic hydrocarbon compounds; preferably, the first solvent includes one or more of tetradecene, hexadecene, octadecene, eicosene, paraffin oil.

[0029] Optionally, in some embodiments of the present application, the chalcogenophenol compound includes one or more of phenylselenol compounds, phenylthiol compounds and phenyltelluride compounds.

[0030] Optionally, in some embodiments of the present application, the phenylselenol compound includes one or more of phenylselenol, diphenyl selenide, diphenyldiselenide; and / or

[0031] The phenylthiol compound includes one or more of phenylthiol, diphenyl sulfide, diphenyldisulfide; and / or

[0032] The phenyltellurium compound includes one or more of phenyltellurol, biphenylditelluride, diphenylditelluride ether.

[0033] Optionally, in some embodiments of the present application, in the silver precursor solution, the concentration range of the silver precursor is 0.1-1 mol / L; and / or

[0034] After the silver precursor solution is heat-treated, the temperature T of the silver precursor solution is 150-280 °C; and / or

[0035] The molar ratio of the anion precursor to the silver precursor in the silver precursor solution is 1:

[0036] (0.5-2); and / or

[0037] The substituents of the substitution include one or more of F, Cl, Br, I;

[0038] And / or, the C 1 -C 10 alkyl group is selected from methyl, ethyl, propyl, butyl;

[0039] And / or, the C 1 -C 10 alkoxy group is selected from methoxy, ethoxy, propoxy, butoxy;

[0040] And / or, the C 1 -C 10 alkylthio group is selected from methylthio, ethylthio, propylthio, butylthio;

[0041] And / or, the C 1 -C 10 alkylcarbonyl group is selected from formyl, acetyl, propionyl, butyryl.

[0042] Optionally, in some embodiments of the present application, after the reaction and before obtaining the silver chalcogenide quantum dots, it further includes: adding a precipitant for precipitation;

[0043] Optionally, the precipitant includes a polar solvent, the polar solvent includes an alcohol solvent, and the alcohol solvent includes one or more of ethanol, methanol, propanol, isopropanol;

[0044] Optionally, the volume ratio of the precipitant to the silver chalcogenide quantum dot stock solution is (1-2):1.

[0045] Optionally, in some embodiments of the present application, the preparation method of the silver precursor solution includes:

[0046] Mixing a silver source, an organic acid and a first solvent, reacting to obtain a silver precursor solution.

[0047] Optionally, in some embodiments of the present application, the silver source includes one or more of silver acetate, silver nitrate, silver sulfate, silver nitrate, silver formate, and silver oxide.

[0048] Optionally, the organic acid includes one or more of oleic acid, butyric acid, n-decanoic acid, hexanoic acid, octanoic acid, dodecanoic acid, myristic acid, palmitic acid, and stearic acid.

[0049] Optionally, in some embodiments of the present application, the molar ratio of the silver source to the organic acid is 1:(1-5).

[0050] Optionally, in some embodiments of the present application, after mixing the silver source, the organic acid, and the first solvent, it further includes: heating to 110-130 °C, and then holding for 0.5-1.5 h.

[0051] Correspondingly, an embodiment of the present application further provides a light-emitting device, including a stacked anode, a light-emitting layer, and a cathode, and the light-emitting layer includes the above-mentioned silver phenylchalcogenide quantum dots.

[0052] Optionally, in some embodiments of the present application, the anode and the cathode each independently include a doped metal oxide particle electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal single-element electrode, or an alloy electrode. The material of the doped metal oxide particle electrode includes one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO 2 / Ag / TiO 2 、TiO 2 / Al / TiO 2 、ZnS / Ag / ZnS or ZnS / Al / ZnS. The material of the metal single-element electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Ca, Mg, and Ba; and / or

[0053] The light-emitting device further includes a hole transport layer and / or a hole injection layer located between the anode and the light-emitting layer. The material of the hole transport layer includes 4,4'-N,N'-dicarbazolyl-biphenyl, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(N-vinylcarbazole) and its derivatives, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine, spiro-NPB, poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexoxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], 1,3-bis(carbazol-9-yl)benzene, polyaniline, polypyrrole, poly(p-)phenylene vinylene, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO 3 , doped or undoped WO 3 , doped or undoped V 2 O 5 , doped or undoped p-type gallium nitride, doped or undoped CrO 3 , doped or undoped CuO, and one or more of them. The material of the hole injection layer includes 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO 3One or more of derivatives thereof, 4,4',4'-tris(N-(3-methylphenyl)-N-phenylamino)triphenylamine, tetracyanoquinodimethane, copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide, and copper oxide; and / or

[0054] The light-emitting device further includes an electron transport layer between the light-emitting layer and the cathode. The material of the electron transport layer includes one or more of inorganic electron transport materials and organic electron transport materials. The inorganic electron transport materials include, but are not limited to, one or more of doped metal oxide particles, undoped metal oxide particles, ceramic semiconductor materials, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The metal oxides in the undoped metal oxide particles include one or more of ZnO, TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 One or more of them. The metal oxides in the doped metal oxide include one or more of ZnO, TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 、Al 2 O 3 One or more of them. The doping elements in the doped metal oxide include one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, Ga, Sn. The IIB-VIA group semiconductor materials include one or more of ZnS, ZnSe, CdS. The IIIA-VA group semiconductor materials include one or more of InP, GaP. The IB-IIIA-VIA group semiconductor materials include one or more of CuInS, CuGaS. The organic electron transport materials include one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds.

[0055] Correspondingly, the present application further provides a display device including the light-emitting device described above.

[0056] The silver phenylchalcogenide quantum dots described in the present application can emit blue-violet light. Description of the Drawings

[0057] To more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the accompanying drawings required for the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present application. For those skilled in the art, without creative efforts, other accompanying drawings can be obtained based on these drawings.

[0058] Figure 1 It is a flowchart of a method for preparing quantum dots provided by an embodiment of the present application;

[0059] Figure 2 It is a schematic structural diagram of a light-emitting device provided by an embodiment of the present application;

[0060] Figure 3 It is a schematic structural diagram of another light-emitting device provided by an embodiment of the present application;

[0061] Figure 4 It is a schematic structural diagram of yet another light-emitting device provided by an embodiment of the present application;

[0062] Figure 5 It is a schematic structural diagram of yet another light-emitting device provided by an embodiment of the present application;

[0063] Figure 6 It is a schematic structural diagram of yet another light-emitting device provided by an embodiment of the present application.

[0064] Reference numerals

[0065] Light-emitting device 100; anode 10; light-emitting layer 20; cathode 30; hole transport layer 40; electron transport layer 50; hole injection layer 60. Detailed implementation manners

[0066] The following will clearly and completely describe the technical solutions in the embodiments of the present application in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, rather than all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts fall within the scope of protection of the present application. In addition, it should be understood that the specific implementation manners described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0067] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" generally refer to the upper and lower in the actual use or working state of the device, specifically the drawing direction in the accompanying drawings; and "inner" and "outer" refer to the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels and do not impose numerical requirements or establish an order.

[0068] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Wherein A and B can be singular or plural.

[0069] In this application, "at least one" means one or more, and "a plurality" means two or more. "At least one kind", "at least one item (piece) below" or similar expressions refer to any combination of these items, including any combination of single item (piece) or plural items (pieces). For example, "at least one item (piece) among a, b, or c", or "at least one item (piece) among a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0070] In this application, when forming another layer "on" a certain layer, the so - called "on" is a broad concept, which can mean that the formed another layer is adjacent to a certain layer, or there are other spacer structure layers between another layer and a certain layer. For example, when forming a second electrode "on" the first carrier functional layer, the so - called "on" can mean that the formed second electrode is adjacent to the first carrier functional layer, or there are other spacer structure layers between the second electrode and the first carrier functional layer, such as a light - emitting layer.

[0071] The various embodiments of this application can exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub - ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub - ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within that range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0072] The technical solution of this application is as follows:

[0073] Please refer to Figure 1 , an embodiment of this application provides a method for preparing silver benzene chalcogenolate quantum dots, including the following steps:

[0074] Step S11: Provide a silver precursor solution and an anion precursor, wherein the anion precursor includes a benzene chalcogenide compound;

[0075] Step S12: Heat-treat the silver precursor solution, and then quickly inject the anion precursor into the silver precursor solution, and react to obtain silver chalcogenobenzoate quantum dots.

[0076] It should be noted that in this application, "chalcogen" in "silver chalcogenobenzoate" and "chalcogenobenzene compound" refers to chalcogen elements, and the chalcogen elements include one of sulfur, selenium, and tellurium.

[0077] The preparation method of the silver chalcogenobenzoate quantum dots described in this application uses a thermal injection method to prepare silver chalcogenobenzoate quantum dots. On the one hand, neither the raw materials nor the products contain heavy metal elements, which is environmentally friendly and low-cost; on the other hand, the process is simple and the reaction temperature is low; on the other hand, the particle size of the prepared silver chalcogenobenzoate quantum dots can be controlled by controlling the reaction temperature, and then the fluorescence wavelength can be controlled, so as to prepare silver chalcogenobenzoate quantum dots that can emit blue-violet light.

[0078] In the step S11:

[0079] The silver precursor solution includes a silver precursor and a first solvent.

[0080] The silver precursor includes but is not limited to silver fatty acid. Further, the silver fatty acid includes but is not limited to one or more of silver oleate, silver butyrate, silver n-decanoate, silver hexanoate, silver octanoate, silver dodecanoate, silver myristate, silver palmitate, and silver stearate.

[0081] The first solvent includes but is not limited to C 10 -C 30 aliphatic hydrocarbon compounds, C 10 -C 30 aromatic hydrocarbon compounds. As an example, the first solvent may include but is not limited to one or more of tetradecene, hexadecene, octadecene, eicosene, and paraffin oil.

[0082] In the silver precursor solution, the concentration range of the silver precursor is 0.1-1 mol / L. For example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, etc. It is beneficial to prepare quantum dots with better performance within this concentration range.

[0083] In some embodiments, the preparation method of the silver precursor solution includes: mixing a silver source, an organic acid, and a first solvent, and reacting the silver source and the organic acid to obtain a silver precursor solution.

[0084] The silver source may include, but is not limited to, one or more of silver acetate, silver nitrate, silver sulfate, silver nitrate, silver formate, and silver oxide.

[0085] The organic acid may include, but is not limited to, one or more of oleic acid, butyric acid, n-decanoic acid, hexanoic acid, octanoic acid, dodecanoic acid, myristic acid, palmitic acid, and stearic acid.

[0086] In some embodiments, the molar ratio of the silver source to the organic acid is 1:(1 - 5), for example, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, etc. Within the range of the molar ratio, it is beneficial for the silver source and the organic acid to fully react and be converted into a silver precursor.

[0087] In some embodiments, after mixing the silver source, the organic acid, and the first solvent, it further includes: heat treatment to enable the silver source and the organic acid to fully react and be converted into a silver precursor.

[0088] In some embodiments, the heat treatment includes: heating from room temperature to 110 - 130 °C, and then holding for 0.5 - 1.5 h.

[0089] In some embodiments, the heat treatment is carried out under vacuum conditions.

[0090] In step S12:

[0091] In some embodiments, the heat treatment of the silver precursor solution is carried out in an inert atmosphere. The gas in the inert atmosphere includes, but is not limited to, one or more of nitrogen, helium, argon, neon, and xenon.

[0092] In some embodiments, after the heat treatment of the silver precursor solution, the temperature of the silver precursor solution is 150 - 280 °C, for example, 150 °C, 180 °C, 200 °C, 220 °C, 250 °C, 260 °C, 280 °C, etc. Within this temperature range, it is beneficial for the silver precursor and the anion precursor to quickly react to generate silver chalcogenide quantum dots.

[0093] The phenyl chalcogenide compound includes, but is not limited to, one or more of phenylseleno compounds, phenylthio compounds, and phenyltelluro compounds.

[0094] The phenylseleno compounds include, but are not limited to, one or more of phenylselenol, diphenyl selenide, and diphenyldiselenide.

[0095] The phenylthio compounds include, but are not limited to, one or more of benzenethiol, diphenyl sulfide, and diphenyldisulfide.

[0096] The phenyltelluro compounds include, but are not limited to, one or more of phenyltellurol, biphenylditelluride, and diphenylditelluride.

[0097] The molar ratio of the anion precursor to the silver precursor in the silver precursor solution is 1:(0.5 - 2), for example, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2, etc. Within this ratio range, it is beneficial for the anion precursor and the silver precursor to fully react, and is beneficial for preparing quantum dots with good crystallization performance and fewer surface defects.

[0098] It can be understood that the reaction solution obtained after the reaction, that is, the silver phenylchalcogenide quantum dot stock solution. In some embodiments, after the reaction and before obtaining the silver phenylchalcogenide quantum dots, it further includes: adding a precipitant to the reaction solution for precipitation and centrifugal separation to obtain the silver phenylchalcogenide quantum dots.

[0099] The precipitant includes but is not limited to polar solvents, the polar solvents include but are not limited to alcohol solvents, and the alcohol solvents include but are not limited to one or more of ethanol, methanol, propanol, and isopropanol.

[0100] The volume ratio of the precipitant to the silver phenylchalcogenide quantum dot stock solution is (1 - 2):1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc. Within this range, it is beneficial to quickly and effectively precipitate the silver phenylchalcogenide quantum dots.

[0101] In a second aspect, the embodiments of the present application further provide silver phenylchalcogenide quantum dots prepared by the above preparation method.

[0102] The structure of the silver phenylchalcogenide quantum dots is shown in formula (I):

[0103]

[0104] Wherein, each occurrence of R is independently selected from H, D, F, Cl, Br, I, or a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 1 -C 10 alkoxy group, a substituted or unsubstituted C 1 -C 10 alkylthio group, a substituted or unsubstituted C 1 -C 10 alkylcarbonyl group, or any combination of the above groups, and not all of R are H; X is selected from S, Se or Te.

[0105] In some embodiments, the substituents of the substitution include one or more of F, Cl, Br, and I.

[0106] In some embodiments, the C 1 -C 10 alkyl group is selected from methyl, ethyl, propyl, and butyl.

[0107] In some embodiments, the C 1 -C 10 alkoxy group is selected from methoxy, ethoxy, propoxy, and butoxy.

[0108] In some embodiments, the C 1 -C 10 alkylthio group is selected from methylthio, ethylthio, propylthio, and butylthio.

[0109] In some embodiments, the C 1 -C 10 alkylcarbonyl group is selected from formyl, acetyl, propionyl, and butyryl.

[0110] The silver phenylchalcogenolate quantum dots can be silver phenylselenate quantum dots (AgSePh quantum dots, AgSeC 6 H 5 quantum dots), silver phenylsulfate quantum dots (silver thiophenolate quantum dots, AgSPh quantum dots, AgSC 6 H 5 quantum dots), or silver phenyltellurate quantum dots (AgTePh quantum dots, AgTeC 6 H 5 quantum dots).

[0111] The average particle size of the silver phenylchalcogenolate quantum dots is 3 to 8 nm, for example, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, etc.

[0112] The emission wavelength of the silver phenylchalcogenolate quantum dots is a blue-violet light wavelength of 380 to 450 nm. Specifically, the emission wavelength of the silver phenylchalcogenolate quantum dots can be 420 nm, 450 nm, 380 nm, 433 nm, 407 nm, 429 nm, 423 nm, 415 nm, 350 nm, 400 nm, 421 nm, 415 nm, 413 nm, etc.

[0113] The fluorescence full width at half maximum of the silver phenylchalcogenolate quantum dots is 30 to 50 nm, for example, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, etc.

[0114] The fluorescence quantum yield of the silver phenylchalcogenate quantum dots is 0.1 to 3.0%, for example, 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.3%, 1.5%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.3%, 2.5%, 2.7%, 2.8%, 3%, etc.

[0115] The silver phenylchalcogenate quantum dots described in this application can emit blue-violet light and do not contain heavy metal elements, which are environmentally friendly and have a wide range of applications.

[0116] In a third aspect, please refer to Figure 2 , this application embodiment also provides a light-emitting device 100, which includes an anode 10, a light-emitting layer 20, and a cathode 30 stacked in sequence. The light-emitting layer 20 includes the silver phenylchalcogenate quantum dots described above.

[0117] Please refer to Figure 3 , in some embodiments, the light-emitting device 100 further includes a hole transport layer 40 located between the anode 10 and the light-emitting layer 20. In other words, the light-emitting device 100 includes an anode 10, a hole transport layer 40, a light-emitting layer 20, and a cathode 30 stacked in sequence.

[0118] Please refer to Figure 4 , in some embodiments, the light-emitting device 100 further includes an electron transport layer 50 located between the light-emitting layer 20 and the cathode 30. In other words, the light-emitting device 100 includes an anode 10, a light-emitting layer 20, an electron transport layer 50, and a cathode 30 stacked in sequence.

[0119] Please refer to Figure 5 , in some embodiments, the light-emitting device 100 includes an anode 10, a hole transport layer 40, a light-emitting layer 20, an electron transport layer 50, and a cathode 30 stacked in sequence.

[0120] Please refer to Figure 6 , in some embodiments, the light-emitting device 100 further includes a hole injection layer 60 located between the anode 10 and the hole transport layer 40.

[0121] The anode 10 and the cathode 30 are an anode and a cathode known in the art for light-emitting devices. For example, they can independently include, but are not limited to, doped metal oxide particle electrodes, composite electrodes, graphene electrodes, carbon nanotube electrodes, elemental metal electrodes, or alloy electrodes. The material of the doped metal oxide particle electrode can include, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO). The composite electrode is a composite electrode in which a metal is sandwiched between doped or undoped transparent metal oxide particles, such as AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO 2 / Ag / TiO 2 、TiO 2 / Al / TiO 2 、ZnS / Ag / ZnS, ZnS / Al / ZnS, etc. Here, " / " represents a laminated structure. For example, AZO / Ag / AZO represents a composite electrode including an AZO layer, an Ag layer, and an AZO layer laminated in sequence. The material of the elemental metal electrode can include, but is not limited to, one or more of Ag, Al, Cu, Mo, Au, Pt, Ca, Mg, and Ba.

[0122] The material of the hole transport layer 40 can also be materials known in the art for hole transport layers, and can include, for example, but not limited to 4,4'-N,N'-dicarbazolyl-biphenyl (CBP), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), poly(N,N' bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (Poly-TPD), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro(spiro-TPD), N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine (DNTPD), 4,4',4'-tris(N-carbazolyl)-triphenylamine (TCTA), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))] (TFB), poly(N-vinylcarbazole) (PVK) and its derivatives, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine (NPB), spiro NPB, poly(phenylene vinylene) (PPV), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV), poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MOMO-PPV), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-omeTAD), 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC), 1,3-bis(carbazol-9-yl)benzene (MCP), polyaniline, polypyrrole, poly(p)phenylene vinylene, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO 3 、doped or undoped WO 3 、doped or undoped V 2 O 5 、doped or undoped p-type gallium nitride, doped or undoped CrO 3One or more of doped or undoped CuO.

[0123] The material of the electron transport layer 50 is a material known in the art for use in an electron transport layer and can be selected from, for example, but not limited to, one or more of inorganic electron transport materials and organic electron transport materials. The inorganic electron transport materials include, but are not limited to, one or more of doped metal oxide particles, undoped metal oxide particles, ceramic semiconductor materials, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The metal oxides in the undoped metal oxide particles include, but are not limited to, one or more of ZnO, TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 One or more of these. The metal oxides in the doped metal oxides include, but are not limited to, one or more of ZnO, TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 、Al 2 O 3 One or more of these. The doping elements in the doped metal oxides include, but are not limited to, one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, Ga, Sn. By way of example, the doped metal oxides can be aluminum-doped zinc oxide (AZO), lithium-doped zinc oxide (LZO), magnesium-doped zinc oxide (MZO), tin-doped zinc oxide (Sn-ZnO), etc. The ceramic semiconductor materials include, but are not limited to, barium titanate. The IIB-VIA group semiconductor materials include, but are not limited to, one or more of ZnS, ZnSe, CdS. The IIIA-VA group semiconductor materials include, but are not limited to, one or more of InP, GaP. The IB-IIIA-VIA group semiconductor materials include, but are not limited to, one or more of CuInS, CuGaS. The organic electron transport materials include one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, hydroxyquinoline compounds.

[0124] The material of the hole injection layer 60 can be a material known in the art for use in a hole injection layer and can be selected from, for example, but not limited to, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN), PEDOT, PEDOT:PSS, PEDOT:PSS doped with a derivative of s-MoO 3 (PEDOT:PSS:s-MoO 3) One or more of 4,4',4'-tris(N-(m-tolyl)-N-phenylamino)triphenylamine (m-MTDATA), tetracyanoquinodimethane (F4-TCQN), copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide, and copper oxide.

[0125] In some embodiments, the thickness of the anode 10 is 20 - 200 nm; the thickness of the light-emitting layer 20 is 30 - 180 nm; the thickness of the cathode 30 is 40 - 190 nm; the thickness of the hole transport layer 40 is 30 - 180 nm; the thickness of the electron transport layer 50 is 10 - 180 nm; the thickness of the hole injection layer 60 is 20 - 200 nm.

[0126] It can be understood that the light-emitting device 100 may further be provided with some functional layers that are commonly used in light-emitting devices and are helpful for improving the performance of the light-emitting device, such as an electron blocking layer, a hole blocking layer, an electron injection layer, an interface modification layer, etc.

[0127] It can be understood that the materials of the respective layers of the light-emitting device 100 can be adjusted according to the light-emitting requirements of the light-emitting device 100.

[0128] In some embodiments, the light-emitting device 100 further includes a substrate, and the substrate is disposed on a side of the anode 10 away from the light-emitting layer 20, or the substrate is disposed on a side of the cathode 30 away from the light-emitting layer 20.

[0129] The substrate may be a rigid substrate or a flexible substrate. In some embodiments, the material of the substrate may include, but is not limited to, one or more of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyethersulfone.

[0130] It can be understood that the light-emitting device 100 may be a normal light-emitting device or an inverted light-emitting device. The light-emitting device 100 may be a quantum dot light-emitting device or an organic light-emitting device.

[0131] The light-emitting layer 20 of the light-emitting device 100 includes quantum dots purified by the purification method described in the present application, thereby having a high light-emitting efficiency and a long lifespan.

[0132] Fourthly, an embodiment of the present application further provides a display device, and the display device includes the light-emitting device 100.

[0133] The display device can be any electronic product with a display function, and the electronic product includes but is not limited to a smart phone, a tablet computer, a laptop computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing scale, a vehicle-mounted display, a television, or an e-book reader. Among them, the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.

[0134] The following is a specific description of the present application through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application.

[0135] Embodiment 1

[0136] Preparation of AgSePh quantum dots:

[0137] Mix 4 mmol of silver acetate, 10 mmol of oleic acid, and 5 mL of 1-octadecene and heat them under vacuum to 120 °C until silver acetate is completely converted to silver oleate to obtain a silver oleate solution, where the content of silver oleate is 4 mmol;

[0138] After changing the reaction atmosphere to argon, raise the temperature to 200 °C;

[0139] Quickly inject 3 mmol of benzeneselenol into the silver oleate solution to obtain the AgSePh quantum dot stock solution;

[0140] Naturally cool to room temperature, precipitate the AgSePh quantum dots by adding ethanol, and collect the precipitate by centrifugation to obtain the AgSePh quantum dots;

[0141] Disperse the AgSePh quantum dots in n-hexane to obtain the AgSePh quantum dot solution.

[0142] Embodiment 2

[0143] This embodiment is basically the same as Embodiment 1, except that in this embodiment, after changing the reaction atmosphere to argon, the temperature is raised to 150 °C.

[0144] Embodiment 3

[0145] This embodiment is basically the same as Embodiment 1, except that in this embodiment, after changing the reaction atmosphere to argon, the temperature is raised to 280 °C.

[0146] Embodiment 4

[0147] This embodiment is basically the same as Embodiment 1, except that in this embodiment, the molar ratio of benzeneselenol to silver oleate is 1:1.

[0148] Embodiment 5

[0149] This example is basically the same as Example 1, except that in this example, the molar ratio of benzeneselenol to silver oleate is 1:0.5.

[0150] Example 6

[0151] This example is basically the same as Example 1, except that in this example, n-decanoic acid is used to replace oleic acid in Example 1.

[0152] Example 7

[0153] This example is basically the same as Example 1, except that in this example, diphenyl diselenide is used to replace benzeneselenol in Example 1.

[0154] Example 8

[0155] This example is basically the same as Example 1, except that in this example, diphenyldiselenide is used to replace benzeneselenol in Example 1.

[0156] Example 9

[0157] This example is basically the same as Example 1, except that in this example, benzenethiol is used to replace benzeneselenol in Example 1, and the corresponding quantum dots prepared in this example are AgSPh quantum dots.

[0158] Example 10

[0159] This example is basically the same as Example 1, except that in this example, biphenylditelluride is used to replace benzeneselenol in Example 1, and the corresponding quantum dots prepared in this example are AgTePh quantum dots.

[0160] Example 11

[0161] This example is basically the same as Example 1, except that in this example, p - p - tolyl diselenide (CAS No. 21856 - 94 - 0) is used to replace benzeneselenol in Example 1, and the corresponding quantum dots prepared in this example are [(4 - methylphenyl)selanyl]silver quantum dots. The structure is as follows:

[0162]

[0163] Example 12

[0164] This example is basically the same as Example 1, except that in this example, bis(2,6 - difluorophenyl)diselane is used to replace benzeneselenol in Example 1, and the corresponding quantum dots prepared in this example are [(1,3 - difluorobenzene - 2 - yl)selanyl]silver quantum dots. The structure is as follows:

[0165]

[0166] Synthesis method of bis(2,6-difluorophenyl) diselenide: Add 33 mmol of Mg to 20 mL of anhydrous tetrahydrofuran (THF), and then add 5.2 mmol of 2-bromo-1,3-difluorobenzene (CAS No. 64248-56-2). Stir the solution for 20 min under a nitrogen atmosphere. After the solvent returns to room temperature, slowly add dropwise a solution of 24.8 mmol of 2-bromo-1,3-difluorobenzene dissolved in 10 mL of THF. Heat the reaction solution to 50 °C and react for 1 h, then cool it to 0 °C using an ice bath. Then add 33 mmol of Se powder to the reaction system at once and gradually heat up. After returning to room temperature, react for another 1 h. After the reaction is completed, filter the product, collect the solvent, and pour it into an ammonium chloride aqueous solution. Add dichloromethane for extraction, wash the organic phase with saturated brine, add anhydrous sodium sulfate for drying, and finally purify it by column chromatography and recrystallization.

[0167] Example 13

[0168] This example is basically the same as Example 1, except that in this example, (1,3,5-trichlorobenzene-2-yl)(2,4,6-trichlorophenyl) diselenide is used to replace phenylselenol in Example 1, and the quantum dots prepared in this example are [(1,3,5-trichlorobenzene-2-yl)seleno] silver quantum dots.

[0169]

[0170] (1,3,5-trichlorobenzene-2-yl)(2,4,6-trichlorophenyl) diselenide synthesis method: Add 33 mmol of Mg to 20 mL of anhydrous tetrahydrofuran (THF), and then add 5.2 mmol of 2-bromo-1,3,5-trichlorobenzene (CAS No. 19393-96-5). Stir the solution for 20 min under a nitrogen atmosphere. After the solvent returns to room temperature, slowly add dropwise a solution of 24.8 mmol of 2-bromo-1,3,5-trichlorobenzene dissolved in 10 mL of THF. Heat the reaction solution to 50 °C and react for 1 h, then cool it to 0 °C using an ice bath. Then add 33 mmol of Se powder to the reaction system at once and gradually heat up. After returning to room temperature, react for another 1 h. After the reaction is completed, filter the product, collect the solvent, and pour it into an ammonium chloride aqueous solution. Add dichloromethane for extraction, wash the organic phase with saturated brine, add anhydrous sodium sulfate for drying, and finally purify it by column chromatography and recrystallization.

[0171] Comparative Example 1

[0172] In this comparative example, known AgSePh nanosheets are used to replace the AgSePh quantum dots in Example 1. The preparation method of the AgSePh nanosheets in this example is as follows:

[0173] Disperse the synthesized 0.5 g of AgSePh bulk in 20 mL of dimethylformamide and perform strong ultrasonic treatment at room temperature for 10 hours. Screen the supernatant by centrifugation to obtain AgSePh nanosheets. Among them, the diameter of the AgSePh nanosheets is about 10 - 20 nm, and the thickness is about 1 - 3 nm.

[0174] Perform TEM particle size, emission wavelength (PL), full width at half maximum, and fluorescence quantum yield (PLQY) tests on the silver phenylchalcogenide quantum dots in Examples 1 - 10 and the AgSePh nanosheets in Comparative Example 1 respectively. The test results are shown in Table 1.

[0175] Among them:

[0176] The TEM particle size is measured by a transmission electron microscope TEM;

[0177] The test method for the emission wavelength (PL) is as follows: Use n - hexane as the solvent, add an appropriate amount of quantum dots or nanosheets, shake well, and then scan in an appropriate wavelength range using a fluorescence spectrophotometer (Hitachi F - 7000), where the excitation wavelength is 350 nm;

[0178] The full width at half maximum is obtained by testing and calculating with a Keithley 2400 high - precision digital source meter, an Ocean Optic USB2000 + spectrometer, and an LS - 160 luminance meter;

[0179] The fluorescence quantum yield (PLQY) is tested using a steady - state fluorescence spectrometer from Edinburgh Instruments, the model of the instrument is FS5, and the accessory corresponding to the measured fluorescence quantum yield is SC - 30.

[0180] Table 1:

[0181]

[0182] As can be seen from Table 1:

[0183] Compared with the AgSePh nanosheets in Comparative Example 1, the silver phenylchalcogenide quantum dots in Examples 1 - 13 have a smaller TEM particle size, a narrower full width at half maximum, and a higher fluorescence quantum yield, and the silver phenylchalcogenide quantum dots in Examples 1 - 13 can emit blue - violet light with a fluorescence wavelength of 380 - 450 nm.

[0184] Device Example 1

[0185] Provide a glass substrate, deposit indium tin oxide (ITO) material on the glass substrate to obtain an ITO anode 10 with a thickness of 80 nm;

[0186] Spin - coat PEDOT:PSS material on the anode 10 and anneal at 150 °C for 20 min to obtain a hole - injection layer 60 with a thickness of 20 nm;

[0187] Spin-coat the TFB material on the hole injection layer 60 and anneal it at 120 °C for 20 min to obtain a hole transport layer 40 with a thickness of 20 nm;

[0188] Spin-coat the quantum dot solution in Example 1 on the hole transport layer 40 to obtain a light-emitting layer 20 with a thickness of 40 nm;

[0189] Spin-coat an ethanol solution of ZnO on the light-emitting layer 20 and anneal it at 80 °C for 20 min to obtain an electron transport layer 50 with a thickness of 35 nm;

[0190] Evaporate Ag on the electron transport layer 50 to obtain a cathode 30 with a thickness of 100 nm;

[0191] Encapsulate to obtain the light-emitting device 100.

[0192] Device Examples 2-13

[0193] Device Examples 2-13 are basically the same as Device Example 1, except that in Device Examples 2-13, the quantum dot solutions in Examples 2-13 are used to replace the quantum dot solution in Example 1.

[0194] Device Comparative Example 1

[0195] Device Comparative Example 1 is basically the same as Device Example 1, except that in Device Comparative Example 1, the AgSePh nanosheets in Comparative Example 1 are used to replace the quantum dots in Example 1.

[0196] Measure the maximum brightness L max 、lifetime T95 and lifetime T95@1000 nit of the light-emitting devices of Device Examples 1-13 and Device Comparative Example 1. The test results are shown in Table 2.

[0197] Maximum brightness L max 、The test methods for lifetime T95 and lifetime T95@1000 nit are as follows: In CDA gas, under the drive of a constant current or voltage, measure the time it takes for the brightness of the device to decay to a certain proportion of the maximum brightness. The time when the brightness decays to 95% of the maximum brightness is defined as T95, and this lifetime is the measured lifetime. To shorten the lifetime test cycle, the device lifetime test is usually carried out by accelerating the device aging at high brightness and fitting the lifetime at low brightness through a decay fitting formula. For example, the lifetime at 1000 nits is denoted as T95@1000 nits, and the calculation formula is:

[0198]

[0199] Among them, T95 LThe lifetime at low brightness is generally taken as the lifetime at 1000 nits, T95 H The lifetime at high brightness, which is the measured lifetime, L H The maximum brightness to which the device is accelerated, L L Generally 1000 nits, A is the acceleration factor, taken as 1.7. Among them, the constant current is 1 mA.

[0200] Table 2:

[0201] <![CDATA[L max (cd / m 2 )]]> T95(h) T95@1000nits(h) Device Example 1 352 0.20 0.16 Device Example 2 541 0.22 0.28 Device Example 3 127 0.10 0.03 Device Example 4 377 0.20 0.16 Device Example 5 321 0.15 0.12 Device Example 6 334 0.13 0.14 Device Example 7 350 0.21 0.14 Device Example 8 327 0.16 0.11 Device Example 9 86 0.05 0.01 Device Example 10 422 0.24 0.06 Device Example 11 344 0.21 0.13 Device Example 12 365 0.25 0.12 Device Example 13 350 0.22 0.15 Device Comparative Example 1 79 0.08 0.001

[0202] As can be seen from Table 2:

[0203] Compared with the light-emitting devices of Comparative Example 1 of the device, the light-emitting devices of Examples 1 to 13 of the device have higher maximum brightness and longer lifetime. It can be seen that the silver phenylchalcogenide quantum dots prepared by the thermal injection method in this application can effectively improve the brightness and lifetime of the light-emitting device when used in the light-emitting device.

[0204] The technical solutions provided in the embodiments of this application have been introduced in detail above. Specific examples are used in this article to elaborate on the principle and implementation manner of this application. The description of the above embodiments is only used to help understand the method and its core idea of this application; at the same time, for those skilled in the art, according to the idea of this application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to this application.

Claims

1. A silver chalcogenobenzoate quantum dot, characterized in that the structure of the silver chalcogenobenzoate quantum dot is shown in formula (I): wherein each occurrence of R is independently selected from H, D, F, Cl, Br, I, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 1 -C 10 alkoxy, substituted or unsubstituted C 1 -C 10 alkylthio, substituted or unsubstituted C 1 -C 10 alkylcarbonyl, or any combination of said groups, and not all of R are H; X is selected from S, Se or Te.

2. The silver chalcogenobenzoate quantum dot according to claim 1, characterized in that the emission wavelength of the silver chalcogenobenzoate quantum dot is 380 - 450 nm; and / or, the substituent of the substitution includes one or more of F, Cl, Br, and I; and / or, said C 1 -C 10 The alkyl group of is selected from methyl, ethyl, propyl, butyl; and / or, said C 1 -C 10 The alkoxy group of is selected from methoxy, ethoxy, propoxy, butoxy; and / or, said C 1 -C 10 alkylthio groups are selected from methylthio, ethylthio, propylthio, butylthio; and / or, said C 1 -C 10 The alkyl carbonyl groups of which are selected from formyl, acetyl, propionyl, butyryl.

3. The silver chalcogenobenzoate quantum dot according to any one of claims 1 - 2, characterized in that the silver chalcogenobenzoate quantum dot includes AgSPh quantum dot, AgSePh quantum dot or AgTePh quantum dot; and / or, the average particle size of the silver chalcogenobenzoate quantum dot is 3 - 8 nm; and / or, the full width at half maximum of the fluorescence of the silver chalcogenobenzoate quantum dot is 30 - 50 nm; and / or, the fluorescence quantum yield of the silver chalcogenobenzoate quantum dot is 0.1 - 3.0%.

4. A preparation method of a silver chalcogenobenzoate quantum dot, characterized in that it includes the following steps: providing a silver precursor solution and an anion precursor, and the anion precursor includes a chalcogenobenzoic compound; heating the silver precursor solution, and then injecting the anion precursor into the silver precursor solution, reacting to obtain a silver chalcogenobenzoate quantum dot; wherein, the structure of the silver chalcogenobenzoate quantum dot is shown in formula (I): Wherein, each occurrence of R is independently selected from H, D, F, Cl, Br, I, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 1 -C 10 alkoxy, substituted or unsubstituted C 1 -C 10 alkylthio, substituted or unsubstituted C 1 -C 10 alkylcarbonyl, or any combination of said groups, and not all of R are H; X is selected from S, Se or Te.

5. The preparation method according to claim 4, characterized in that the silver precursor solution includes a silver precursor and a first solvent; optionally, the silver precursor includes a fatty acid silver; preferably, the fatty acid silver includes one or more of silver oleate, silver butyrate, silver decanoate, silver hexanoate, silver octanoate, silver dodecanoate, silver myristate, silver palmitate, and silver stearate; Optionally, the first solvent includes C 10 -C 30 aliphatic hydrocarbon compounds, C 10 -C 30 aromatic hydrocarbon compounds, or one or more of them; preferably, the first solvent includes one or more of tetradecene, hexadecene, octadecene, eicosene, and paraffin oil.

6. The preparation method according to claim 4, characterized in that the chalcogenobenzoic compound includes one or more of a benzeneselenyl compound, a benzenethiol compound, and a benzenetelluride compound; optionally, the benzeneselenyl compound includes one or more of benzeneselenol, diphenyl diselenide, and diphenyldiselenide; optionally, the benzenethiol compound includes one or more of benzenethiol, diphenyl sulfide, and diphenyldisulfide; optionally, the benzenetelluride compound includes one or more of benzenetellurol, biphenyl ditelluride, and diphenylditelluride.

7. The preparation method according to claim 4, characterized in that in the silver precursor solution, the concentration range of the silver precursor is 0.1 - 1 mol / L; and / or, after heating the silver precursor solution, the temperature of the silver precursor solution is 150 - 280 °C; and / or, the molar ratio of the anion precursor to the silver precursor in the silver precursor solution is 1:(0.5 - 2); and / or, the substituent of the substitution includes one or more of F, Cl, Br, and I; and / or, said C 1 -C 10 The alkyl group of is selected from methyl, ethyl, propyl, butyl; and / or, said C 1 -C 10 The alkoxy group of is selected from methoxy, ethoxy, propoxy, butoxy; and / or, said C 1 -C 10 alkylthio groups are selected from methylthio, ethylthio, propylthio, butylthio; and / or, said C 1 -C 10 The alkyl carbonyl groups of which are selected from formyl, acetyl, propionyl, butyryl; and / or, after the reaction and before obtaining the silver chalcogenobenzoate quantum dot, it further includes: adding a precipitant for precipitation; optionally, the precipitant includes a polar solvent, and the polar solvent includes an alcohol solvent, and the alcohol solvent includes one or more of ethanol, methanol, propanol, and isopropanol; Optionally, the volume ratio of the precipitating agent to the stock solution of silver chalcogenide quantum dots is (1-2):

1.

8. The preparation method according to claim 4, characterized in that the preparation method of the silver precursor solution comprises: mixing a silver source, an organic acid and a first solvent, and reacting to obtain a silver precursor solution; Optionally, the silver source includes one or more of silver acetate, silver nitrate, silver sulfate, silver nitrate, silver formate and silver oxide; Optionally, the organic acid includes one or more of oleic acid, butyric acid, n-decanoic acid, hexanoic acid, octanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid.

9. The preparation method according to claim 8, characterized in that the molar ratio of the silver source to the organic acid is 1:(1-5); and / or after mixing the silver source, the organic acid and the first solvent, it further comprises: heating to 110-130 °C, and then holding for 0.5-1.5 h.

10. A light-emitting device, characterized in that the light-emitting layer of the light-emitting device includes the silver chalcogenide quantum dots according to any one of claims 1-3, or the light-emitting layer of the light-emitting device includes the silver chalcogenide quantum dots prepared by the preparation method according to any one of claims 4-9.

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