Quantum dot precursor, preparation method thereof and quantum dot

Abstract

The invention discloses a quantum dot precursor, a preparation method thereof and a quantum dot, and relates to the field of quantum dots. The structural formula of the quantum dot precursor is as shown in a formula (I): # imgabs0 #. The quantum dot precursor provided by the invention is high in stability.

Description

Technical Field

[0001] The present application relates to the technical field of quantum dots, and particularly relates to a quantum dot precursor, a preparation method thereof, and a quantum dot. Background Art

[0002] Quantum dots have the advantages of saturated emission light color and adjustable wavelength, and high photoluminescence and electroluminescence quantum yields, and are widely used in the field of display technology.

[0003] Generally, quantum dots are synthesized from quantum dot precursors, and the quantum dot precursors are closely related to the stability of quantum dots. At present, the preparation method of quantum dot precursors is relatively complex, and the prepared quantum dot precursors have poor stability and need to be further improved. Summary of the Invention

[0004] In view of this, the present application provides a quantum dot precursor, a preparation method thereof, and a quantum dot.

[0005] The embodiments of the present application are implemented as follows. A quantum dot precursor, the structural formula of the quantum dot precursor is shown in formula (I):

[0006]

[0007] Wherein, M is selected from metals;

[0008] R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted heterocyclic group with 3 to 20 ring atoms, or one or more of them;

[0009] R3, R4, R5, R6, and R7 each independently include hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms;

[0010] The heteroatoms in the heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic groups include one or more of N, S, O, P, and Si;

[0011] The substituents of the substitution each independently include one or more of -NH, -F, -Cl, -Br, -I, -OH, -COOH, -NO, -SO H, -CHO, -SH, -OH, -OOCCH3, and -CN.

[0012] Optionally, in some embodiments of the present application, R1 and R2 are selected from hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 5 to 15 ring atoms; and / or

[0013] R3, R4, R5, R6, and R7 are selected from hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, one or more of substituted or unsubstituted heterocyclic groups having 5 to 15 ring atoms.

[0014] Optionally, in some embodiments of the present application, the R1 is selected from C2-C 18 alkyl; and / or

[0015] the R2 is selected from substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7; optionally, the R2 is selected from -N(C2H5)2, -OC 16 H 33 , -SC 16 H 33 , -NHC 16 H 33 , -P(OC 16 H 33 )2; and / or

[0016] the M is selected from divalent metals; optionally, the divalent metal is selected from one of Zn, Cd, Pb, Hg, Cu, Ni, Mn.

[0017] Optionally, in some embodiments of the present application, the quantum dot precursor includes one of the following formulas:

[0018]

[0019]

[0020] Correspondingly, the embodiments of the present application also provide a method for preparing a quantum dot precursor, including:

[0021] providing a dispersion liquid, the dispersion liquid includes compound A and a solvent, and the structural formula of the compound A is shown in formula (II):

[0022] Compound B is provided, and the chemical formula of the compound B is R9-NH2. The compound B and the dispersion liquid are mixed and reacted to obtain a quantum dot precursor;

[0023] Wherein, M is selected from metals; R8 and R9 are each independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted heterocyclic group with 3 to 20 ring atoms, or one or more of them; R3, R4, R5, R6, and R7 each independently include hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted heterocyclic group with 3 to 20 ring atoms, or one or more of them; the heteroatoms in the heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic group include one or more of N, S, O, P, and Si; the substituents of the substitution each independently include -NH, -F, -Cl, -Br, -I, -OH, -COOH, -NO, -SO H, -CHO, -SH, -OH, -OOCCH3, -CN, or one or more of them.

[0024] Optionally, in some embodiments of the present application, R1 and R2 are selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, substituted or unsubstituted heterocyclic group with 5 to 15 ring atoms, one or more of them; R3, R4, R5, R6, and R7 are selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, substituted or unsubstituted heterocyclic group with 5 to 15 ring atoms, one or more of them;

[0025] Optionally, R1 is selected from C2-C 18 alkyl; and / or

[0026] Optionally, R2 is selected from substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7; and / or

[0027] Optionally, R2 is selected from -N(C2H5)2, -OC 16 H 33, -SC 16 H 33 , -NHC 16 H 33 , -P(OC 16 H 33 )2, or one of the following:

[0028] Optionally, in some embodiments of the present application, the compound A includes M(DDTC)2,

[0029]

[0030] , or one of the following; and / or

[0031] the compound B includes one of n-octylamine, ethylamine, heptylamine, ethylamine, butylamine, dodecylamine, octadecylamine; and / or

[0032] the solvent includes octadecene.

[0033] Optionally, in some embodiments of the present application, in the dispersion liquid, the molar concentration of the compound A is 0.05 mmol / mL to 0.2 mmol / mL; and / or

[0034] the molar ratio of the compound A to the compound B is 1:(1 - 4); and / or

[0035] the mixing of the compound A and the compound B is carried out under bubbling; and / or

[0036] the reaction of the compound A and the compound B is carried out at room temperature; and / or

[0037] the reaction time of the compound A and the compound B is 2 min to 15 min;

[0038] the method for mixing the compound B and the dispersion liquid includes: adding the compound B to the dispersion liquid in batches.

[0039] Correspondingly, the embodiments of the present application further provide a quantum dot, which is prepared from the above-mentioned quantum dot precursor, or is prepared from the quantum dot precursor obtained by the above-mentioned preparation method.

[0040] Optionally, in some embodiments of the present application, the quantum dot includes a core-shell structure quantum dot, and the shell layer of the core-shell structure quantum dot is prepared from the above-mentioned quantum dot precursor, or is prepared from the quantum dot precursor obtained by the above-mentioned preparation method; and / or

[0041] the quantum dot includes a blue quantum dot.

[0042] The quantum dot precursor provided by the present application has high stability and consistency. Brief Description of the Drawings

[0043] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0044] Figure 1 is a flowchart of a method for preparing a quantum dot precursor provided by an embodiment of the present application;

[0045] Figure 2 is a nuclear magnetic resonance hydrogen spectrum of the quantum dot precursor provided in Embodiments 1-4 and Comparative Example 1 of the present application;

[0046] Figure 3 is an external view of the quantum dot precursor provided in Embodiment 1 and Comparative Example 1 of the present application;

[0047] Figure 4 Photoluminescence spectra provided by Quantum Dot Embodiment 1 and Quantum Dot Comparative Example 1 of the present application. Detailed Description of the Embodiments

[0048] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the 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 of 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 embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0049] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" usually refer to the upper and lower in the actual use or working state of the device, specifically the drawing direction in the drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of the present application, the term "including" 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.

[0050] In the present application, "and / or" describes the association relationship of associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. Where A and B can be singular or plural.

[0051] In this application, "at least one" means one or more, and "a plurality" means two or more. "One or several", "at least one (item)" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one (item) of a, b, or c", or "at least one (item) of 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 each be single or multiple.

[0052] Various embodiments of this application may 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 described 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 the 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.

[0053] Currently, preparing quantum dot precursors requires high - temperature treatment, and the temperature needs to be maintained at 60°C to 100°C throughout the reaction process until the reaction ends; moreover, it requires a large number of reaction devices, resulting in a large amount of economic and time costs; in addition, high temperature will accelerate the oxidation process, affecting the stability and consistency of quantum dot precursors.

[0054] The technical solution of this application is as follows:

[0055] In a first aspect, an embodiment of this application provides a quantum dot precursor, and the structural formula of the quantum dot precursor is shown as formula (Ⅰ):

[0056]

[0057] Among them, M is selected from metals;

[0058] R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1 - C 32 alkyl, substituted or unsubstituted C1 - C 32 heteroalkyl, substituted or unsubstituted C2 - C 32 alkenyl, substituted or unsubstituted C2 - C 32 heteroalkenyl, substituted or unsubstituted C2 - C 32 alkynyl, substituted or unsubstituted C2 - C 32The heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms; the heteroatoms in the heteroalkyl, heteroalkenyl, and heteroalkynyl include one or more of N, S, O, P, and Si;

[0059] R3, R4, R5, R6, and R7 each independently include hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms;

[0060] the heteroatoms in the heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic groups include one or more of N, S, O, P, and Si;

[0061] The substituents of the substitution each independently include one or more of -NH, -F, -Cl, -Br, -I, -OH, -COOH, -NO, -SO H, -CHO, -SH, -OH, -OOCCH3, and -CN.

[0062] The quantum dot precursor provided in this application contains S element and can be used as a sulfur source for synthesizing quantum dots; the chain lengths of R1 and R2 in the quantum dot precursor can be adjusted, and the selection range of the quantum dot precursor is wide; moreover, the preparation method of the quantum dot precursor is simple, which can improve the stability and consistency of the quantum dot precursor.

[0063] In some embodiments, the M is selected from divalent metals.

[0064] Further, the divalent metal is selected from one of Zn, Cd, Pb, Hg, Cu, Ni, and Mn.

[0065] In some embodiments, R1 and R2 are selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 5 to 15 ring atoms.

[0066] In some embodiments, R1 and R2 are selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C 10 -C 15 alkyl, substituted or unsubstituted C 10 -C 15 heteroalkyl, substituted or unsubstituted C 10 -C 15 alkenyl, substituted or unsubstituted C 10 -C 15 heteroalkenyl, substituted or unsubstituted C 10 C 15 alkynyl, substituted or unsubstituted C 10 -C 15 heteroalkynyl, substituted or unsubstituted C 10 -C 15 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C5-C 15 acyloxy, substituted or unsubstituted C5-C 15 alkoxycarbonyl, substituted or unsubstituted C 10 -C 15 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 10 to 15 ring atoms.

[0067] In some embodiments, R3, R4, R5, R6, and R7 are selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 5 to 15 ring atoms.

[0068] In some embodiments, R3, R4, R5, R6, and R7 are selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C 10 -C 15 alkyl, substituted or unsubstituted C 10 -C 15 heteroalkyl, substituted or unsubstituted C 10 -C 15 alkenyl, substituted or unsubstituted C 10 -C 15 heteroalkenyl, substituted or unsubstituted C 10 -C 15 alkynyl, substituted or unsubstituted C 10 -C 15 heteroalkynyl, substituted or unsubstituted C 10 -C 15 alkoxy, substituted or unsubstituted C 10 -C 15 acyloxy, substituted or unsubstituted C 10 -C 15 alkoxycarbonyl, substituted or unsubstituted C 10 -C 15 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 10 to 15 ring atoms.

[0069] In some embodiments, the halogen includes one or more of fluorine, chlorine, bromine, and iodine.

[0070] The alkyl includes one or more of methyl, ethyl, isopropyl, tert-butyl, and n-octyl.

[0071] The alkenyl group includes one or more of vinyl, propenyl, and butenyl.

[0072] The alkynyl group includes one or more of ethynyl, propynyl, pentynyl, and heptynyl.

[0073] The alkoxy group includes one or more of methoxy, ethoxy, and propoxy.

[0074] The acyloxy group includes one or more of formyloxy, acetyloxy, propionyloxy, butyryloxy, octanoyloxy, palmitoyloxy, and stearoyloxy.

[0075] The alkoxycarbonyl group includes one or more of methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, octoxycarbonyl, palmitoxycarbonyl, and stearoxycarbonyl.

[0076] The aryl group includes one or more of phenyl, p-tolyl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, and p-nitromethoxyphenyl.

[0077] Preferably, the R1 is selected from C2-C 18 alkyl.

[0078] Preferably, the R2 is selected from substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, and substituted or unsubstituted -PR6R7.

[0079] In some embodiments, the R2 is selected from one of -N(C2H5)2, -OC 16 H 33 -SC 16 H 33 -NHC 16 H 33 -P(OC 16 H 33 )2.

[0080] Exemplarily, the quantum dot precursor includes one of the following formulas:

[0081]

[0082]

[0083] In a second aspect, referring to Figure 1 , the present application further provides a method for preparing a quantum dot precursor, including:

[0084] S11. Provide a dispersion liquid, where the dispersion liquid includes compound A and a solvent, and the structural formula of the compound A is shown in formula (II):

[0085] S12. Provide compound B, the chemical formula of the compound B is R9-NH2, mix the compound B and the dispersion liquid, and react to obtain a quantum dot precursor;

[0086] Among them, M is selected from metals; R8 and R9 are each independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted heterocyclic group with 3 to 20 ring atoms, or one or more of them; the heteroatoms in the heteroalkyl, heteroalkenyl, and heteroalkynyl include one or more of N, S, O, P, and Si; R3, R4, R5, R6, and R7 each independently include hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20one or more of aryl, substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms; the heteroatoms in the heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic groups include one or more of N, S, O, P, and Si; the substituents of the substitution each independently include one or more of -NH, -F, -Cl, -Br, -I, -OH, -COOH, -NO, -SOH, -CHO, -SH, -OH, -OOCCH3, and -CN.

[0087] It should be noted that the method for preparing the quantum dot precursor provided in this application can be carried out at room temperature, and the reaction vessel can be a sample bottle.

[0088] The method for preparing the quantum dot precursor provided in this application simplifies the raw materials and reaction devices, reduces the cost, and the reaction does not require heating, improving the stability of the quantum dot precursor, being not easily oxidized, and thus improving the synthesis consistency of the quantum dot precursor.

[0089] The material selection of M refers to the above description, and the selection of R8 and R9 can refer to R1 and R2 respectively, which will not be elaborated here.

[0090] In some embodiments, the compound A includes M(DDTC)2 (diethyldithiocarbamate), one of them.

[0091] In some embodiments, the compound B includes one of n-octylamine, ethylamine, heptylamine, ethylamine, butylamine, dodecylamine, and octadecylamine.

[0092] In some embodiments, the solvent includes octadecene (ODE). It can be understood that the selection of the solvent is also simplified, further saving the preparation cost of the quantum dot precursor.

[0093] In some embodiments, in the dispersion liquid, the molar concentration of the compound A is 0.05 mmol / mL to 0.2 mmol / mL, and can be, for example, 0.08 mmol / mL, 0.1 mmol / mL, 0.12 mmol / mL, 0.15 mmol / mL, etc. Within the range of the molar concentration, it is beneficial to the uniform dispersion of the compound A.

[0094] In some embodiments, the molar ratio of the compound A to the compound B is 1:(1 - 4), and can be, for example, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, etc. Within the range of the molar ratio, it is beneficial to improve the yield of the quantum dot precursor.

[0095] In some embodiments, the mixing of Compound A and Compound B is carried out under bubbling. It can be understood that under the action of bubbling, it is beneficial for Compound A and Compound B to be fully mixed and contacted to generate a quantum dot precursor.

[0096] In some embodiments, the reaction between Compound A and Compound B is carried out at room temperature.

[0097] In some embodiments, the reaction time between Compound A and Compound B is 2 min to 15 min, for example, it can be 4 min, 6 min, 8 min, 10 min, 12 min, 14 min, etc.

[0098] In some embodiments, the method for mixing Compound B and the dispersion includes: adding Compound B to the dispersion in batches. It can be understood that mixing in batches can make the reaction rate controllable and improve the reaction uniformity.

[0099] Specifically, first add a part of Compound B to the dispersion, and after reacting for a period of time, then add the remaining part of the organic matter.

[0100] Exemplarily, when Compound A is Zn(DDTC)2, the reaction formula of Zn(DDTC)2 and Compound B is as follows:

[0101]

[0102] In a third aspect, the present application also provides a quantum dot, which is prepared from the above-mentioned quantum dot precursor.

[0103] It can be understood that the quantum dot precursor provided by the present application can be used for synthesizing quantum dots, specifically, for preparing the shell layer of core-shell quantum dots.

[0104] Preferably, the quantum dot is a blue quantum dot. It can be understood that blue quantum dots have poor stability and short lifespan, and there is an urgent need for improvement. Using the quantum dot precursor provided by the present application to synthesize blue quantum dots can effectively improve the stability of blue quantum dots and extend their service life.

[0105] Exemplarily, the method for synthesizing quantum dots includes:

[0106] Adding the quantum dot precursor provided by the present application to the solution in which the quantum dot core has been synthesized; reacting to form a quantum dot shell on the surface of the quantum dot core to obtain a quantum dot.

[0107] It should be noted that the shell layer of the core-shell structure quantum dot is one or more layers, and the quantum dot precursor provided by the present application can be used for synthesizing any shell layer.

[0108] The present application will be specifically described below through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application.

[0109] Example 1

[0110] This example provides a quantum dot precursor, and its structural formula is as follows:

[0111] Its preparation method is as follows:

[0112] Place a magnetic stir bar into a 20 mL sample bottle, weigh 1 mmol of Zn(DDTC)2 and place it in the sample bottle, then add 10 mL of ODE; after bubbling at room temperature for 5 - 10 minutes, add 1 mmol of n-octylamine, add 1 mmol of n-octylamine after reacting for 2 minutes, and then stop the reaction after reacting for another 2 minutes until the solution is completely dissolved to obtain a quantum dot precursor mixed solution; purify the quantum dot precursor by column chromatography. Fill 300-mesh silica gel into a glass column, tap both sides of the glass column to make the silica gel packed tightly. The height of the silica gel column is about 15 cm. Pour the quantum dot precursor mixed solution onto the upper surface of the silica gel column, use chlorobenzene as the eluent, and perform separation after repeated elution multiple times to obtain the target product quantum dot precursor.

[0113] Examples 2 - 6

[0114] Examples 2 - 6 are basically the same as Example 1, except that in Examples 2 - 6, Zn(DDTC)2 is respectively replaced with Cd(DDTC)2, Ni(DDTC)2.

[0115] Examples 7 - 8

[0116] Examples 7 - 8 are basically the same as Example 1, except that in Examples 7 - 8, n-octylamine is respectively replaced with octadecylamine and ethylamine.

[0117] Examples 9 - 10

[0118] Examples 9 - 10 are basically the same as Example 1, except that

[0119] In Example 9, a total of 4 mmol of n-octylamine is added, and the addition method is: add 1 mmol of n-octylamine, add 1 mmol of n-octylamine after reacting for 2 minutes, add 1 mmol of n-octylamine after reacting for another 2 minutes, and add 1 mmol of n-octylamine after reacting for another 2 minutes.

[0120] In Example 10, a total of 1 mmol of n-octylamine is added, and the addition method is: add 1 mmol of n-octylamine and react for 2 minutes.

[0121] Examples 11 - 12

[0122] Examples 11 to 12 are basically the same as Example 1, except that

[0123] in Example 11, the reaction was carried out for 1 min each time after adding n-octylamine, and the total reaction time was 2 min;

[0124] in Example 12, the reaction was carried out for 7.5 min each time after adding n-octylamine, and the total reaction time was 15 min.

[0125] Comparative Example 1

[0126] This comparative example provides a quantum dot precursor, and its preparation method includes:

[0127] Place a magnetic stir bar in a 100 ml three-necked flask, add 16 ml of ODE (octadecene) and 34 ml of OAm (oleylamine), evacuate at room temperature for 20 min, and slowly heat up to 120 °C and continue to evacuate for 20 min after no obvious bubbles;

[0128] After no obvious bubbles, add 3.44 g of Zn(Ac)2, maintain the vacuum environment, and start to cool down after complete dissolution and no bubbles;

[0129] When the temperature drops to 60 °C, add 2.26 g of Zn(DDTC)2, maintain the vacuum environment and continue the reaction until Zn(DDTC)2 completely reacts to obtain the quantum dot precursor.

[0130] Measure the 1H NMR spectra of the quantum dot precursors prepared in Examples 1 to 4 and Comparative Example 1, and the results are as Figure 2 shown. Take pictures to record the appearance states of the quantum dot precursors prepared in Example 1 and Comparative Example 1, and the results are shown Figure 3 as follows.

[0131] It can be seen from Figure 2 that between the chemical shifts of 0.8 ppm to 1.0 ppm, the peak of Comparative Example 1 is relatively weak, while the peaks of Examples 1 to 4 are more obvious, indicating that the desired quantum dot precursor is prepared by the preparation method provided in this application.

[0132] It can be seen from Figure 3 that Example 1 was not heated at high temperature, and the prepared quantum dot precursor is a relatively transparent emulsion, while the quantum dot precursor prepared in Comparative Example 1 was heated at high temperature, and the reaction raw materials were oxidized, showing light yellow and unstable in nature.

[0133] Quantum Dot Example 1

[0134] This quantum dot example provides a blue quantum dot, and the preparation method is as follows:

[0135] Add 20 mmol of Zn(OA)2 solution to a three-necked flask, evacuate to no bubbles at 150 °C, switch to an argon atmosphere for protection, heat up to 330 °C, inject 1 mmol of Se DPP precursor, and then inject 0.12 mmol of Cd(OA)2 precursor after 1 min, and react for 2 h;

[0136] Slowly inject 3 mmol of Se TOP, and the injection time is 2 h. After the reaction is completed, cool down to 310 °C;

[0137] Simultaneously inject 2 mmol of S TOP and 0.6 mmol of Cd(OA)2, and the injection time is 20 min. After the reaction is completed, cool down to 120 °C;

[0138] Inject 0.25 mmol of the quantum dot precursor solution of Example 1, and the injection time is 5 min, and then cool down to 120 °C;

[0139] Take 40 mL of n-hexane and 40 mL of ethyl acetate in a centrifuge tube, pour the above solution into the centrifuge tube, then add 60 ml of ethanol, shake well and centrifuge, and the precipitate is the quantum dot.

[0140] Quantum Dots Example 2 - 12

[0141] Quantum Dots Example 2 - 12 are basically the same as Quantum Dots Example 1, except that the quantum dot precursor of Example 1 is replaced with the quantum dot precursors of Examples 2 - 12 respectively.

[0142] Quantum Dots Comparative Example 1

[0143] Quantum Dots Comparative Example 1 is basically the same as Quantum Dots Example 1, except that the quantum dot precursor of Example 1 is replaced with the quantum dot precursor of Comparative Example 1.

[0144] Prepare quantum dots 50 times each according to the methods of Quantum Dots Example 1 - 12 and Quantum Dots Comparative Example 1, and measure the PL intensity (photoluminescence spectrum) and EL intensity (electroluminescence spectrum) of each quantum dot; the photoluminescence spectra of Quantum Dots Example 1 and Quantum Dots Comparative Example 1 are as Figure 3 shown. The wavelength average value ± standard deviation, and the full width at half maximum average value ± standard deviation of Quantum Dots Example 1 - 12 and Quantum Dots Comparative Example 1 are shown in Table 1.

[0145] Table 1

[0146]

[0147] As can be seen from Table 1:

[0148] It can be obtained from Quantum Dot Examples 1 to 12 and Quantum Dot Comparative Example 1 that the maximum standard deviation of the PL wavelength of Quantum Dot Examples 1 to 12 is 0.5, and the maximum standard deviation of the PL full width at half maximum is 0.4. While in Quantum Dot Comparative Example 1, the standard deviation of the PL wavelength is 3.2, and the maximum standard deviation of the PL full width at half maximum is 3.2, indicating that Quantum Dot Comparative Example 1 is extremely unstable, and the quantum dot precursor affects the stability and consistency of Quantum Dot Comparative Example 1;

[0149] Correspondingly, for the electroluminescence spectrum, the maximum standard deviation of the EL wavelength of Quantum Dot Examples 1 to 12 is 0.4, and the maximum standard deviation of the EL full width at half maximum is 0.3. While in Quantum Dot Comparative Example 1, the standard deviation of the EL wavelength is 2.5, and the maximum standard deviation of the EL full width at half maximum is 1.0; The quantum dot precursor provided in this application has not been heat-treated, has relatively stable self-performance and high consistency, so it correspondingly improves the consistency and stability of the quantum dots prepared therefrom.

[0150] The above has introduced in detail the quantum dot precursor provided in the embodiments of the present application, its preparation method, and the quantum dots. Specific examples are used herein to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; At the same time, for those skilled in the art, according to the idea of the present 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 the present application.

Claims

1. A quantum dot precursor, characterized in that, The structural formula of the quantum dot precursor is shown in Formula (I): Wherein, M is selected from metals; R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, formyl, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms; R3, R4, R5, R6, and R7 each independently include hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms; The heteroatoms in the heteroalkyl group, heteroalkenyl group, heteroalkynyl group, and heterocyclic group include one or more of N, S, O, P, and Si; The substituents of the substitution each independently include one or more of -NH, -F, -Cl, -Br, -I, -OH, -COOH, -NO, -SO H, -CHO, -SH, -OH, -OOCCH3, and -CN.

2. The quantum dot precursor according to claim 1, wherein R1 and R2 are selected from hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, formyl, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms, or one or more of them; and / or R3, R4, R5, R6, and R7 are selected from hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, aldehyde, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, or one or more of substituted or unsubstituted heterocyclic groups having 5 to 15 ring atoms.

3. The quantum dot precursor according to claim 1, wherein The R1 is selected from C2-C 18 alkyl; and / or R2 is selected from substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7; optionally, R2 is selected from -N(C2H5)2, -OC 16 H 33 、-SC 16 H 33 、-NHC 16 H 33 、-P(OC 16 H 33 )2; and / or M is selected from divalent metals; optionally, the divalent metal is selected from one of Zn, Cd, Pb, Hg, Cu, Ni, and Mn.

4. The quantum dot precursor according to claim 1, wherein The quantum dot precursor includes one of the following formulas:

5. A preparation method of a quantum dot precursor, characterized in that, Including: A dispersion is provided, which includes Compound A and a solvent, and the structural formula of Compound A is as shown in Formula (II): Providing compound B, the chemical formula of compound B is R9-NH2, mixing compound B and the dispersion liquid, and reacting to obtain a quantum dot precursor; Among them, M is selected from metals; R8 and R9 are each independently selected from hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, formyl, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, or one or more of these; R3, R4, R5, R6, and R7 each independently include hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, formyl, nitro, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 heteroalkyl, substituted or unsubstituted C2-C 32 alkenyl, substituted or unsubstituted C2-C 32 heteroalkenyl, substituted or unsubstituted C2-C 32 alkynyl, substituted or unsubstituted C2-C 32 heteroalkynyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C1-C 32 acyloxy, substituted or unsubstituted C1-C 32 alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, or one or more of these; the heteroatoms in the heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic groups include one or more of N, S, O, P, and Si; the substituents of the substituted groups each independently include one or more of -NH, -F, -Cl, -Br, -I, -OH, -COOH, -NO, -SO H, -CHO, -SH, -OH, -OOCCH3, and -CN.

6. The preparation method according to claim 5, wherein R1 and R2 are selected from the group consisting of hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, formyl, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms, one or more of them; R3, R4, R5, R6, and R7 are selected from the group consisting of hydrogen, deuterium, halogen, cyano, hydroxy, carboxy, formyl, nitro, substituted or unsubstituted C5-C 20 alkyl, substituted or unsubstituted C5-C 20 heteroalkyl, substituted or unsubstituted C5-C 20 alkenyl, substituted or unsubstituted C5-C 20 heteroalkenyl, substituted or unsubstituted C5-C 20 alkynyl, substituted or unsubstituted C5-C 20 heteroalkynyl, substituted or unsubstituted C5-C 20 alkoxy, substituted or unsubstituted C3-C 20 acyloxy, substituted or unsubstituted C5-C 20 alkoxycarbonyl, substituted or unsubstituted C8-C 20 aryl, substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms, one or more of them; Optionally, the R1 is selected from C2-C 18 alkyl; and / or Optionally, R2 is selected from substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted -NR3R4, substituted or unsubstituted -SR5, substituted or unsubstituted -PR6R7; and / or Optionally, R2 is selected from -N(C2H5)2, -OC 16 H 33 , -SC 16 H 33 , -NHC 16 H 33 , -P(OC 16 H 33 )2.

7. The preparation method according to claim 5, wherein The compound A includes one of M(DDTC)2, and / or Compound B includes one of n-octylamine, ethylamine, heptylamine, ethylamine, butylamine, dodecylamine, and octadecylamine; and / or The solvent includes octadecene.

8. The preparation method according to claim 5, wherein In the dispersion liquid, the molar concentration of compound A is 0.05 mmol / mL to 0.2 mmol / mL; and / or The molar ratio of compound A to compound B is 1:(1 to 4); and / or The mixing of compound A and compound B is carried out under bubbling; and / or The reaction of compound A and compound B is carried out at room temperature; and / or The reaction time of compound A and compound B is 2 min to 15 min; The method for mixing compound B and the dispersion liquid includes: adding compound B to the dispersion liquid in batches.

9. A quantum dot, characterized in that, Prepared from the quantum dot precursor according to any one of claims 1 to 4, or prepared from the quantum dot precursor prepared by the preparation method according to any one of claims 5 to 8.

10. The quantum dot according to claim 9, wherein The quantum dot includes a core-shell structure quantum dot, and the shell layer of the core-shell structure quantum dot is prepared from the quantum dot precursor according to any one of claims 1 to 4, or prepared from the quantum dot precursor prepared by the preparation method according to any one of claims 5 to 8; and / or The quantum dot includes a blue quantum dot.

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