CN117126669A - ZnSe (Te) quantum dot, preparation method thereof and electroluminescent device - Google Patents
ZnSe (Te) quantum dot, preparation method thereof and electroluminescent device Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 166
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 halogen ions Chemical class 0.000 claims abstract description 38
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 58
- 229910001507 metal halide Inorganic materials 0.000 claims description 35
- 150000005309 metal halides Chemical class 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical group CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 229910003363 ZnMgO Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- FQVPFGDPYSIWTM-UHFFFAOYSA-N tributyl(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCP(=S)(CCCC)CCCC FQVPFGDPYSIWTM-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- PIOZWDBMINZWGJ-UHFFFAOYSA-N trioctyl(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCCCCCP(=S)(CCCCCCCC)CCCCCCCC PIOZWDBMINZWGJ-UHFFFAOYSA-N 0.000 description 1
- GAAKLDANOSASAM-UHFFFAOYSA-N undec-10-enoic acid;zinc Chemical compound [Zn].OC(=O)CCCCCCCCC=C GAAKLDANOSASAM-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940118257 zinc undecylenate Drugs 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The application discloses a ZnSe (Te) quantum dot, which comprises a quantum dot core, wherein the quantum dot core comprises halogen ions X doped in the quantum dot core ‑ The quantum dot core comprises a cation and an anion, and the halogen ion X ‑ Combined with the cations. According to the application, halogen X is doped in the core of ZnSe (Te) quantum dot, so that ZnSe quantum dot with fluorescence emission wavelength above 430nm and ZnSeTe quantum dot with fluorescence emission wavelength above 480nm are obtained, and the quantum efficiency of the quantum dot is high (more than or equal to 75 percent), and the quantum dot can be applied in multiple fields. In addition, the preparation method provided by the application is simple and convenient to operate, short in reaction time and high in efficiency, and meets the requirement of large-scale production of quantum dots.
Description
Technical Field
The application belongs to the field of quantum dots, and particularly relates to a ZnSe (Te) quantum dot, a preparation method thereof and an electroluminescent device.
Background
In the prior art, the emission wavelength of the common ZnSe-based quantum dots is generally smaller than 430nm, which limits the application of the ZnSe-based quantum dots in the wavelength range above 430 nm. By introducing Te elements to construct ZnSeTe quantum dots, the emission wavelength of the quantum dots can be extended to 532nm, but the quantum yield of the quantum dots obtained by the method is not high, and the further application of the quantum dots is affected.
Based on the above problems, a novel quantum dot based on ZnSe and a preparation method thereof are needed to be researched, so that the type of the current lead-free and cadmium-free quantum dot is expanded, and meanwhile, the application range of the quantum dot based on ZnSe is expanded.
Disclosure of Invention
In view of the above, the present application aims to provide a ZnSe (Te) quantum dot having an emission wavelength ranging from 430nm to 580nm and a method for preparing the same, which have high quantum yield and expand the application range of ZnSe-based quantum dots in the prior art.
In order to achieve the above purpose, the application adopts the following technical scheme:
a first object of the present application is to provide a ZnSe (Te) quantum dot comprising a quantum dot core comprising a halogen ion X doped in the quantum dot core - The quantum dot core comprises a cation and an anion, and the halogen ion X - Combined with the cations.
Specifically, the halogen ion is selected from F - 、Cl - 、Br - 、I - At least one of them.
Specifically, the quantum dot further comprises a shell layer coated outside the quantum dot core, wherein the shell layer is one selected from ZnS, znSe, znSeS, znSe/ZnS and ZnSeS/ZnS.
Preferably, the quantum dot core is ZnSe, and the emission wavelength of the quantum dot is 430-480nm.
Preferably, the quantum dot core is ZnSeTe, and the emission wavelength of the quantum dot is 480-580nm.
The second object of the present application is to provide a method for preparing ZnSe (Te) quantum dots, comprising the steps of:
s1, obtaining the quantum dot core;
s2, mixing a coordination solution of metal halide with the quantum dot core at a first temperature, and reacting to obtain a first mixed solution containing the quantum dot core;
s3, adding a zinc precursor and a sulfur precursor into the first mixed solution, and coating a shell layer on the quantum dot core at a second temperature to obtain the quantum dot.
Specifically, the feeding mole ratio of the quantum dot core to the coordination solution of the metal halide is 1 (1-10).
Specifically, the coordination solution of the metal halide is at least one of amine, phosphine or carboxylic acid solutions of the metal halide;
preferably, the coordination solution of the metal halide is trioctylphosphine or oleylamine solution of the metal halide, and the metal halide is at least one selected from zinc halide, magnesium halide, calcium halide, iron halide or manganese halide.
Specifically, in S2, the first temperature is 180-320 ℃, and the concentration of the coordination solution of the metal halide is (0.04-0.4) mol/L.
Specifically, the feeding molar ratio between the zinc precursor, the sulfur precursor and the quantum dot core is (1.8-3): 1.8-3:1;
the zinc precursor is at least one selected from zinc carboxylate, zinc halide or organic zinc;
the sulfur precursor is at least one selected from an organophosphorus complex of sulfur, a fatty amine compound of sulfur and a long-chain alkene solution of sulfur;
the second temperature is 230-320 ℃.
A third object of the present application is to provide an electroluminescent device comprising a light emitting layer comprising ZnSe (Te) quantum dots as described above or ZnSe (Te) quantum dots prepared by the preparation method as described above.
Compared with the prior art, the application has at least the following advantages:
according to the application, halogen X is doped in the core of ZnSe (Te) quantum dot, so that ZnSe quantum dot with fluorescence emission wavelength above 430nm and ZnSeTe quantum dot with fluorescence emission wavelength above 480nm are obtained, and the quantum efficiency of the quantum dot is high (more than or equal to 75 percent), and the quantum dot can be applied in multiple fields. In addition, the preparation method provided by the application is simple and convenient to operate, short in reaction time and high in efficiency, and meets the requirement of large-scale production of quantum dots.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the comparison of fluorescence emission spectra of example 2 and example 3;
FIG. 2 is a graph showing the comparison of fluorescence emission spectra of example 9 and example 15.
Detailed Description
The technical solutions in the examples will be described in detail below in connection with the embodiments of the present application. It should be noted that this embodiment is only a partial way, not an entire way.
At least one of the "when preceding or following a list of elements" as for example "is described herein modifies the entire list of elements without modifying individual elements of the list. Unless otherwise defined, all terms (including technical and scientific terms) in the specification can be defined as commonly understood by one of ordinary skill in the art. Terms defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Furthermore, unless expressly stated to the contrary, the words "comprise" and the words "comprising" when used in this specification mean the presence of stated features, regions, integers, steps, operations, elements, and/or components, but does not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof. Accordingly, the above phraseology is to be understood as meaning to include the stated elements, but not to exclude any other elements.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The term "or" means "and/or".
It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms.
As used herein, "about" or "approximately" includes the stated values and is meant to be within an acceptable range of deviation from the particular values as determined by one of ordinary skill in the art in view of the measurements in question and the errors associated with the measurement of the particular quantities (i.e., limitations of the measurement system). For example, "about" may mean that the deviation from the stated value is within one or more standard deviations, or within + -10%, + -5%.
In the prior art, the emission wavelength of the common ZnSe-based quantum dots is generally smaller than 430nm, which limits the application of the ZnSe-based quantum dots in the wavelength range above 430 nm. By introducing Te elements to construct ZnSeTe quantum dots, the emission wavelength of the quantum dots can be extended to 480nm, but the quantum yield of the quantum dots obtained by the method is not high, and the further application of the quantum dots is affected. The application provides a quantum dot and a preparation method thereof for solving the problems in the prior art.
The first object of the present application is to provide a ZnSe (Te) quantum dot comprising a quantum dot core comprising a halogen ion X doped in the quantum dot core, a shell layer coating the quantum dot core - The quantum dot core comprises cations and anions, and halogen ions X - Combined with cations. Specifically halogen ion X - With cationic Zn 2+ The dangling bond of the quantum dot core surface is passivated. The shell layer is one selected from ZnS, znSe, znSeS, znSe/ZnS and ZnSeS/ZnS. Halogen ion is selected from F - 、Cl - 、Br - 、I - In the present application, the halide ions originate from a coordination solution of the metal halide.
The surface of the quantum dot provided by the application contains the ligand, and the ligand can keep the quantum dot stable. The ligand can be various, and the ligand common in the prior art can be adopted, and oil-soluble or water-soluble ligand can be selected according to the requirement.
In one embodiment of the application, the quantum dot core is ZnSe, the emission wavelength of the quantum dot is 430-480nm, the quantum yield can reach 75% at most, and the difficulty in preparing ZnSe-based quantum dot with the emission wavelength of 430-480nm in the prior art is overcome.
In another embodiment of the application, the quantum dot core is ZnSeTe, the emission wavelength of the quantum dot is 480-580nm, the quantum yield is more than or equal to 75%, and the problem of the reduction of the quantum yield when the wavelength is improved in the prior art is solved.
The application also provides a preparation method of the ZnSe (Te) quantum dot, which comprises the following steps:
s1, obtaining the quantum dot core;
s2, mixing the coordination solution of the metal halide with the quantum dot core at the first temperature of 180-320 ℃ to react to obtain a first mixed solution containing the quantum dot core; the feeding mole ratio of the quantum dot core to the coordination solution of the metal halide is 1 (1-10); the concentration of the coordination solution of the metal halide is (0.04-0.4) mol/L;
s3, adding a zinc precursor and a sulfur precursor into the first mixed solution, and coating a shell layer outside a quantum dot core at a second temperature of 230-320 ℃ to obtain the quantum dot; the molar ratio of zinc precursor, sulfur precursor and quantum dot core is (1.8-3) (1).
According to the application, through the limitation of the feeding mole ratio of the quantum dot core to the metal halide coordination solution, the metal halide coordination solution fully reacts with the quantum dot core, so that halogen ions are doped into and/or on the quantum dot core, thereby passivating metal cations and preventing the metal cations from being oxidized. When the coordination solution of the metal halide is excessive, the solution can emit white light, and the quantum yield is low; too little complexing solution of the metal halide may result in insufficient participation of the halide ions in the reaction, failing to meet the requirements of the present application.
The coordination solution of the metal halide is at least one of amine, phosphine or carboxylic acid solutions of the metal halide; preferably, the complexing solution of the metal halide is a trioctylphosphine or oleylamine solution of the metal halide, and the metal halide is at least one selected from zinc halide, magnesium halide, calcium halide, iron halide or manganese halide.
The zinc precursor is at least one selected from zinc carboxylate, zinc halide or organic zinc; preferably, the zinc precursor is at least one selected from zinc powder, zinc oxide, zinc chloride, zinc oxalate, zinc acetate, zinc carbonate, zinc stearate, zinc acetylacetonate, diethyl zinc, zinc undecylenate, zinc tetradecanoate, and zinc oleate.
The sulfur precursor is at least one selected from the group consisting of an organophosphorus complex of sulfur, a fatty amine compound of sulfur, and a long-chain alkene solution of sulfur. Preferably, the sulfur precursor is at least one selected from the group consisting of sulfur powder, a tetradecene solution of sulfur, a pentadecene solution of sulfur, a hexadecene solution of sulfur, a heptadecene solution of sulfur, an octadecene solution of sulfur, an n-octylamine solution of sulfur, a tri-n-octylamine solution of sulfur, trioctylphosphine sulfide, tributylphosphine sulfide, 1-octylmercaptan, 1-dodecylmercaptan, a mixture of 1-octylmercaptan and tri-n-octylamine, and a mixture of 1-octylmercaptan and tributylphosphine.
The wavelength can be increased by doping Te in ZnSe quantum dots, and the mass percent of Te doped in the application is not more than 5 percent. According to the application, by doping halogen X in the core of the ZnSe (Te) quantum dot, on the basis of obtaining the ZnSe quantum dot with fluorescence emission wavelength more than 430nm and the ZnSe quantum dot with fluorescence emission wavelength more than 480nm, the quantum efficiency of the quantum dot is not reduced, and the application range of the ZnSe (Te) quantum dot can be enlarged.
In the present application, the quantum dot core ZnSe or ZnSeTe can be prepared by any known method or can be commercially available. The preparation process of the quantum dots is carried out under inert gas atmosphere. In some preferred embodiments of the present application, the inert gas is at least one of nitrogen, argon, and the like.
In some preferred embodiments of the present application, the method for preparing quantum dots further comprises the steps of precipitating and purifying the prepared quantum dots by using a purifying agent. These steps are well known in the art and are not described in detail herein.
The third object of the application is to provide an electroluminescent device comprising a luminescent layer comprising ZnSe (Te) quantum dots as above or ZnSe (Te) quantum dots prepared by the preparation method as above.
An electroluminescent device comprises a light-emitting layer, wherein the light-emitting layer comprises the ZnSe (Te) quantum dots or the ZnSe (Te) quantum dots prepared by the preparation method. The preparation of the light-emitting layer and the electroluminescent device may be carried out by methods known in the art.
The present application will be described in detail with reference to specific examples.
Example 1
The embodiment provides a preparation method of ZnSe/ZnS quantum dots, which comprises the following specific steps:
s1, obtaining quantum dot core ZnSe;
s2, at the first temperature of 240 ℃,2.5mmol 0.1M ZnCl 2 Mixing TOP solution of (2) with 0.5mmol quantum dot core, and reacting for 30min to obtain a first mixed solution containing quantum dot core;
s3, adding 1mmol of zinc stearate and 1mmol of n-dodecyl mercaptan into the first mixed solution, and purifying at the second temperature of 240 ℃ under the condition that the quantum dot core is coated with a shell layer, thereby obtaining the quantum dot ZnSe/ZnS doped with chlorine in the quantum dot core.
The quantum dots ZnSe/ZnS obtained by the preparation are prepared into the ITO/PEDOT/TFB/QD/ZnMgO/Al of the electroluminescent device, and the preparation method adopts a conventional method in the prior art and is not repeated here.
The Cl content of the quantum dot obtained in example 1 was 1004.8ppm by cleaning the quantum dot core ZnSe and then measuring by using the GB/T34672-2017 method.
Example 2
This example provides a method for preparing ZnSe/ZnS quantum dots, which is substantially the same as example 1, except that 0.5mmol 0.1M ZnCl is added in the S2 step 2 TOP solution of (C).
Example 3
This example provides a method for preparing ZnSe/ZnS quantum dots, which is substantially the same as example 1, except that in the S2 step, 5mmol of 0.1M ZnCl is added 2 TOP solution of (C).
Example 4
The present embodiment provides a ZnSe/ZnS quantum dotThe preparation process is essentially the same as in example 1, except that in step S2, znBr is used as the complexing solution for the metal halide 2 The TOP solution of (2) to obtain the quantum dot ZnSe/ZnS doped with bromine in the quantum dot core.
Example 5
The present example provides a method for preparing ZnSe/ZnS quantum dots, which is substantially the same as that of example 1, except that in the S2 step, the coordination solution of the metal halide is ZnI 2 The TOP solution of (2) to obtain the quantum dot ZnSe/ZnS doped with iodine in the quantum dot core.
Example 6
The present example provides a method for preparing ZnSe/ZnS quantum dots, which is substantially the same as that of example 1, except that in the S2 step, 2.5mmol 0.4M ZnCl is used as the complexing solution for the metal halide 2 Is a solution of oleylamine of (a).
Example 7
The present example provides a method for preparing ZnSe/ZnS quantum dots, which is substantially the same as that of example 1, except that in the S2 step, 2.5mmol 0.4M ZnCl is used as the complexing solution for the metal halide 2 TOP solution of (C).
Example 8
The present example provides a method for preparing ZnSe/ZnS quantum dots, which is substantially the same as that of example 1, except that in the S2 step, 2.5mmol 0.04M ZnCl is used as the complexing solution for the metal halide 2 TOP solution of (C).
Example 9
The embodiment provides a preparation method of ZnSeTe/ZnS quantum dots, which comprises the following specific steps:
s1, obtaining a quantum dot core ZnSeTe, wherein the mass percentage of Te doped in the quantum dot core is 3%;
s2, at the first temperature of 200 ℃, 3.5mmol 0.1M ZnCl 2 Mixing TOP solution of (2) with 0.5mmol quantum dot core, and reacting for 30min to obtain a first mixed solution containing quantum dot core;
s3, adding 1mmol of zinc stearate and 1mmol of n-dodecyl mercaptan into the first mixed solution, and purifying at the second temperature of 240 ℃ under the condition that the quantum dot core is coated with a shell layer, thereby obtaining the quantum dot ZnSeTe/ZnS doped with chlorine in the quantum dot core.
The quantum dots ZnSeTe/ZnS obtained by the preparation method are prepared into the ITO/PEDOT/TFB/QD/ZnMgO/Al of the electroluminescent device, and the preparation method adopts a conventional method in the prior art and is not repeated here.
Example 10
This example provides a method for preparing ZnSeTe/ZnS quantum dots substantially as in example 9, except that in step S2, the reaction takes place at a first temperature of 180 ℃.
Example 11
This example provides a method for preparing ZnSeTe/ZnS quantum dots substantially as in example 9, except that in step S2, the reaction takes place at a first temperature of 320 ℃.
Example 12
This example provides a method for preparing ZnSeTe/ZnS quantum dots substantially as described in example 9, except that 3.5mmol 0.1M MgCl is selected as the complexing solution for the metal halide 2 TOP solution of (C).
Example 13
This example provides a method for preparing ZnSeTe/ZnS quantum dots substantially as in example 9, except that 0.05mmol 0.1M ZnCl is added in the S2 step 2 TOP solution of (C).
Example 14
This example provides a method for preparing ZnSeTe/ZnS quantum dots substantially as in example 9, except that 0.5mmol 0.1M ZnCl is added in the S2 step 2 TOP solution of (C).
Example 15
This example provides a method for preparing ZnSeTe/ZnS quantum dots substantially as in example 9, except that in the S2 step 5mmol of 0.1M ZnCl is added 2 TOP solution of (C).
Example 16
This example provides a preparation method of ZnSeTe/ZnS quantum dots, which is substantially the same as that of example 9, except that in step S1, quantum dot cores ZnSeTe are obtained, wherein the mass percentage of Te doped in the quantum dot cores is 1%.
Comparative example 1.
The comparative example provides a preparation method of ZnSe/ZnS quantum dots, which comprises the following specific steps: obtaining quantum dot core ZnSe; adding 1mmol of zinc stearate and 1mmol of n-dodecyl mercaptan into 0.5mmol of quantum dot core ZnSe, coating a shell layer outside the quantum dot body at the second temperature of 240 ℃, and purifying to obtain the quantum dot ZnSe/ZnS.
Comparative example 2.
The comparative example provides a preparation method of ZnSeTe/ZnS quantum dots, which comprises the following specific steps: obtaining 0.5mmol quantum dot core ZnSeTe; adding 1mmol of zinc stearate and 1mmol of n-dodecyl mercaptan into the quantum dot core ZnSeTe, and purifying at the second temperature of 240 ℃ in the outer cladding layer of the quantum dot body to obtain the quantum dot ZnSeTe/ZnS.
The ZnSe (Te) Quantum Dots (QDs) obtained in examples 1-16 and comparative examples 1-2 were prepared as electroluminescent devices ITO/PEDOT/TFB/QD/ZnMgO/Al, respectively, and their fluorescence spectra and fluorescence quantum yields were tested.
The specific test results are shown in the following table:
the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A ZnSe (Te) quantum dot comprising a quantum dot core, characterized in that: the quantum dot core comprises halogen ion X doped in the quantum dot core - The quantum dot core comprises a cation and an anion, and the halogen ion X - Combined with the cations.
2. The ZnSe (Te) quantum dot of claim 1, wherein: the quantum dot further comprises a shell layer coated outside the quantum dot core, wherein the shell layer is one selected from ZnS, znSe, znSeS, znSe/ZnS and ZnSeS/ZnS.
3. The ZnSe (Te) quantum dot of claim 2, wherein: the quantum dot core is ZnSe, and the emission wavelength of the quantum dot is 430-480nm.
4. The ZnSe (Te) quantum dot of claim 2, wherein: the quantum dot core is ZnSeTe, and the emission wavelength of the quantum dot is 480-580nm.
5. The preparation method of the ZnSe (Te) quantum dot is characterized by comprising the following steps of:
s1, obtaining the quantum dot core according to any one of claims 1-4;
s2, mixing a coordination solution of metal halide with the quantum dot core at a first temperature, and reacting to obtain a first mixed solution containing the quantum dot core;
and S3, adding a zinc precursor and a sulfur precursor into the first mixed solution, and coating a shell layer on the quantum dot core at a second temperature to obtain the quantum dot.
6. The method for preparing ZnSe (Te) quantum dots according to claim 5, wherein: the feeding mole ratio of the quantum dot core to the coordination solution of the metal halide is 1 (0.1-10).
7. The method for preparing ZnSe (Te) quantum dots according to claim 5, wherein: the coordination solution of the metal halide is at least one of amine, phosphine or carboxylic acid solutions of the metal halide;
preferably, the coordination solution of the metal halide is trioctylphosphine or oleylamine solution of the metal halide, and the metal halide is at least one selected from zinc halide, magnesium halide, calcium halide, iron halide or manganese halide.
8. The method for preparing ZnSe (Te) quantum dots according to claim 5, wherein: in S2, the first temperature is 180-320 ℃, and the concentration of the coordination solution of the metal halide is (0.04-0.4) mol/L.
9. The method for preparing ZnSe (Te) quantum dots according to claim 5, wherein: the molar ratio of the zinc precursor to the sulfur precursor to the quantum dot core is (1.8-3): 1;
the zinc precursor is at least one selected from zinc carboxylate, zinc halide or organic zinc;
the sulfur precursor is at least one selected from an organophosphorus complex of sulfur, a fatty amine compound of sulfur and a long-chain alkene solution of sulfur;
the second temperature is 230-320 ℃.
10. An electroluminescent device comprising a light emitting layer, characterized in that: the luminescent layer comprises ZnSe (Te) quantum dots according to any one of claims 1 to 4 or ZnSe (Te) quantum dots prepared by the preparation method according to any one of claims 5 to 9.
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| WO2021054650A2 (en) * | 2019-09-18 | 2021-03-25 | 주식회사 한솔케미칼 | Method for manufacturing quantum dots and quantum dots manufactured thereby |
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| TWI237314B (en) * | 2004-06-24 | 2005-08-01 | Ind Tech Res Inst | Doping method for forming quantum dots |
| US20150291422A1 (en) * | 2014-04-11 | 2015-10-15 | Korea Institute Of Machinery & Materials | Quantum dot stabilized by halogen salt and method for manufacturing the same |
| CN106566529A (en) * | 2016-11-10 | 2017-04-19 | Tcl集团股份有限公司 | Passivated quantum dot and preparation method thereof |
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