CN112048300B - Cadmium-free quantum dot, preparation method thereof and quantum dot photoelectric device - Google Patents

Cadmium-free quantum dot, preparation method thereof and quantum dot photoelectric device Download PDF

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CN112048300B
CN112048300B CN201910486192.4A CN201910486192A CN112048300B CN 112048300 B CN112048300 B CN 112048300B CN 201910486192 A CN201910486192 A CN 201910486192A CN 112048300 B CN112048300 B CN 112048300B
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高静
袁秀玲
乔培胜
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Najing Technology Corp Ltd
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Abstract

The invention discloses a cadmium-free quantum dot, a preparation method thereof and a quantum dot photoelectric device. The cadmium-free quantum dot comprises a nanocrystal core, wherein the nanocrystal core comprises a first InZnP core and a second InZnP core coated outside the first InZnP core, and the element proportion of the components of the first InZnP core and the second InZnP core is the same or different. In the prepared cadmium-free quantum dot, the uniformity of the nanocrystal core is good, and the core-shell quantum dot prepared by the nanocrystal core has narrow half-peak width, high quantum efficiency and good stability.

Description

Cadmium-free quantum dot, preparation method thereof and quantum dot photoelectric device
Technical Field
The invention relates to the technical field of quantum dot materials, in particular to a cadmium-free quantum dot, a preparation method thereof and a quantum dot photoelectric device.
Background
The quantum dots are also called semiconductor nanocrystals, and have the advantages of adjustable light-emitting wavelength, high light-emitting efficiency, good stability and the like, so that the quantum dots are widely applied to the fields of display, illumination, biology, solar cells and the like. In recent years, research on II-VI group quantum dot materials containing CdSe, cdS and the like has been greatly advanced, the efficiency, half-peak width, stability and other properties of the quantum dot materials are greatly improved, and the quantum dot materials are applied to the fields of display, biology and the like. However, since Cd is a toxic heavy metal, the european union "legislation on chemical registration, evaluation, permission and restriction" (REACH for short) strictly regulates the Cd content in goods entering the market, and its wide application is limited, so people never give up on research on environment-friendly cadmium-free quantum dots. How to improve the performance of the cadmium-free quantum dots is always a key point and a difficult point of research. In cadmium-free quantum dots, III-V group InP-based quantum dots become a research hotspot and are expected to replace Cd-containing quantum dots.
The InP-based quantum dots in the prior art have the main problems of low fluorescence quantum yield, large luminescence half-peak width (low color purity) and poor light, heat and water stability which are main reasons for restricting the application of the InP-based quantum dots. How to reduce the half-peak width is always a hotspot and difficulty in the research of cadmium-free quantum dots.
Thick Shell InP-ZnSe Quantum Dots (> 5 nm) prepared by Kemar R.Reid et al have half-widths around 40nm and fluorescence efficiencies around 40% (reference: chemical Structure, ensemble and Single-Particle Spectroscopy of thickness-Shell InP-ZnSe Quantum Dots: nano Lett.2018,18, 709-716).
The half-width of the emission peak of Quantum Dots prepared by Parthiban Ramasamy et al by adopting a Two-Step 'Seed-medium' method is 37nm at 533nm, the efficiency is 65 +/-2%, the half-width of the emission peak is 36nm at 550nm, and the efficiency is 60 +/-3% (refer to Two-Step 'Seed-medium' Synthetic Approach to Colloidal Indium phosphate Dots with High-Purity Photo-and electrorheological center, chem. Mater.2018,30, 3643-3647).
In the prior art, a Zn element is doped in an InP core, but the uniformity of zinc doping in the existing InZnP core is poor, so that the half-peak width of the InZnP core is wider, and the half-peak width of a core-shell quantum dot obtained after a shell layer is coated is wider. Such as: sungjun Koh et al compared two zinc doping methods, one is to mix an In precursor and a P precursor at high temperature to form InP, and then add a Zn precursor to form an InZnP core. The half-peak width of the quantum dots prepared by the method is more than 60nm. And the other method is to mix a Zn precursor and a P precursor to form a Zn-P compound firstly and then form an InZnP core with an In precursor, and the quantum dot prepared by the method has improved half-peak width but is still larger than 40nm. (reference: zinc-phosphor Complex Working as an organic Valve for Colloidal Growth of Monodissperse Indium Phosphide Quantum Dots, chem. Mater.2017,29, 6346-6355). Parthiban Ramasamy et al synthesized InZnP green quantum dots by a one-step method (i.e., mixing an In precursor, a Zn precursor, a ligand and ODE, then adding a P precursor, and heating up to 305 ℃ for nucleation.) have a half-peak width of 36-38nm and an efficiency of 67-71%, and the method is amplified, and when the yield is 1.63g of In (Zn) P/ZnSe/ZnS quantum dots, the half-peak width is increased to 40nm and the efficiency is reduced to 64%. ( Reference: tunable, bright, and Narrow Luminescence from Colloidal Indium phosphate Quantum Dots, chem.Mater.2017,29,6893-6899 )
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a cadmium-free quantum dot with narrow half-peak width, high quantum efficiency and high stability and a preparation method thereof.
According to one aspect of the invention, a cadmium-free quantum dot is provided, which comprises a nanocrystal core, wherein the nanocrystal core comprises a first InZnP core and a second InZnP core coated outside the first InZnP core, and the element ratios of the components of the first InZnP core and the second InZnP core are the same or different.
In one embodiment, the cadmium-free quantum dot further comprises a shell layer, and the shell layer comprises ZnSe coated outside the nanocrystal core x S 1-x And x is more than 0 and less than or equal to 1, the fluorescence emission wavelength of the cadmium-free core-shell quantum dot is adjustable within the range of 500-550 nm, the fluorescence half-peak width is less than or equal to 35nm, and the quantum efficiency is more than or equal to 60%.
In one embodiment, the first exciton peak position of the first InZnP core is adjustable in a range of 380-440 nm.
In one embodiment, the shell further comprises ZnSe coated on the surface of the shell x S 1-x And a ZnS layer outside the layer.
According to another aspect of the present invention, there is provided a method for preparing cadmium-free quantum dots, comprising the steps of:
s1, preparing a solution containing a first InZnP nucleus;
s2, adding InZnP growth liquid containing InZnP clusters into the solution containing the first InZnP nuclei to grow second InZnP nuclei outside the first InZnP nuclei so as to obtain nanocrystal nuclei, wherein the InZnP growth liquid containing the InZnP clusters is prepared by the following method: and reacting a second reaction system including a second indium precursor, a second zinc precursor, and a second phosphorus precursor at 25 to 150 ℃ to obtain the InZnP growth solution containing the InZnP cluster.
In one embodiment, in the step S1, a first reaction system including a first indium precursor, a first zinc precursor, and a first phosphorus precursor is reacted at 150 to 330 ℃ to prepare the first InZnP nucleus-containing solution, and preferably, the first reaction system is reacted at 180 to 300 ℃.
In one embodiment, the ratio of the amount of the indium element in the first indium precursor to the amount of the phosphorus element in the first phosphorus precursor is 1.
In one embodiment, the ratio of the amount of indium element in the first indium precursor to the amount of zinc element in the first zinc precursor is 1.
In one embodiment, in the InZnP growth liquid containing the InZnP cluster, a ratio of the amount of the indium element in the second indium precursor to the amount of the phosphorus element in the second phosphorus precursor is 1 to 2.
In one embodiment, the ratio of the amount of indium in the second indium precursor to the amount of zinc in the second zinc precursor is 1.
In one embodiment, after the step S2, the method further includes a step S3: at least one ZnSe is coated outside the nanocrystal core x S 1-x Layer, wherein x is more than 0 and less than or equal to 1.
In one embodiment, after the step S3, the method further includes a step S4: in the above ZnSe x S 1-x And a ZnS layer is coated outside the layer.
According to another aspect of the present invention, there is provided a quantum dot optoelectronic device comprising the aforementioned cadmium-free quantum dots.
Compared with the prior art, the cadmium-free quantum dot prepared by the method has the advantages that the uniformity of the nanocrystal core is good, and the core-shell quantum dot prepared by the cadmium-free quantum dot has the advantages of narrow half-peak width, high quantum efficiency and good stability.
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The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows the aging stability of the quantum dot film of example 1 under different conditions;
fig. 2 shows the aging stability of the quantum dot membrane of comparative example 1 under different conditions.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances in order to facilitate the description of the embodiments of the application herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a cadmium-free quantum dot, which comprises a nanocrystal core, wherein the nanocrystal core comprises a first InZnP core and a second InZnP core coated outside the first InZnP core, and the element proportions of the components of the first InZnP core and the second InZnP core are the same or different.
In the prior art, zn is doped in an InP core, but the conventional InZnP core is synthesized by adopting a one-step method, and the inventor finds that the homogeneity of zinc doping in the InZnP core synthesized by adopting the one-step method is poor, so that the half-peak width of the InZnP core is wider, and the half-peak width of the core-shell quantum dot obtained after coating a shell layer is wider (more than or equal to 36 nm). In order to solve the above problems, the present invention provides a nanocrystal core, which comprises a first InZnP core and a second InZnP core that are synthesized step by step, wherein the second InZnP core is coated outside the first InZnP core.
In some embodiments, the first exciton peak position of the first InZnP nanocrystal core is tunable in the range of 380 to 440nm. In some embodiments, the cadmium-free quantum dot further comprises a shell layer comprising ZnSe coated over the nanocrystalline core x S 1-x Layer, wherein x is more than 0 and less than or equal to 1. By coating the shell layer outside the nanocrystal core, the core-shell quantum dot with green light emission can be obtained, the fluorescence emission wavelength of the core-shell quantum dot is adjustable within the range of 500-550 nm, the fluorescence half-peak width of the core-shell quantum dot is less than or equal to 35nm, and the quantum efficiency of the core-shell quantum dot is more than or equal to 60%.
It will be appreciated by those skilled in the art that the variation in fluorescence emission wavelength can be achieved by adjusting the size of the nanocrystal core, shell, or the ratio of elements in the composition of the cadmium-free quantum dot.
In some embodiments, the shell further comprises cladding ZnSe x S 1-x And a ZnS layer outside the layer.
The invention also provides a preparation method of the cadmium-free quantum dot, which comprises the following steps:
s1, preparing a solution containing a first InZnP nucleus;
s2, adding InZnP growth liquid containing InZnP clusters into the solution containing the first InZnP nucleus to grow a second InZnP nucleus outside the first InZnP nucleus so as to obtain a nanocrystal core, wherein the InZnP growth liquid containing the InZnP clusters is prepared by the following method: and reacting a second reaction system comprising a second indium precursor, a second zinc precursor and a second phosphorus precursor at 25-150 ℃ to prepare the InZnP growth solution containing the InZnP clusters.
The invention provides a method capable of preparing a nanocrystal core comprising two InZnP cores (namely a first InZnP core and a second InZnP core), wherein the half-peak width ratio of the nanocrystal core is narrower than that of the InZnP core synthesized by a one-step method, and the stability is better.
In some embodiments, in step S1, a first reaction system comprising a first indium precursor, a first zinc precursor, and a first phosphorus precursor is reacted at 150 to 330 ℃ to produce a solution comprising a first InZnP nucleus. Preferably, the first reaction system is reacted at 180 to 300 ℃ to produce a solution containing a first InZnP nucleus.
In some embodiments, the first indium precursor may be, but is not limited to, a long chain acid indium, the first zinc precursor may be, but is not limited to, a long chain zinc salt, and the first phosphorus precursor may be, but is not limited to, one or more of tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, tris (diethylamine) phosphine, tris (dimethylamine) phosphine.
In some embodiments, the first indium precursor and the first zinc precursor are prepared by: mixing an indium precursor, a first ligand, a zinc precursor and a first non-coordinating solvent to form a first mixed solution. Preferably, the indium precursor, the first ligand, the zinc precursor, and the first non-coordinating solvent are mixed, and the mixture is heated to 150 to 330 ℃ to react to form a first mixed solution, and preferably heated to 180 to 300 ℃ to react to form a first mixed solution. The first mixed solution includes a first indium precursor and a first zinc precursor. Wherein the indium precursor may be, but is not limited to, inCl 3 、In(MA) 3 、In(Ac) 3 Can be, but is not limited to, zn (Ac) 2 、Zn(MA) 2 、Zn(St) 2 、Zn(OA) 2 One or more of (a).
In some embodiments, the first phosphorus precursor is prepared by: and mixing the phosphorus precursor, the second ligand and the second non-coordinating solvent to form a second mixed solution. The second mixed solution includes a first phosphorus precursor. Wherein, the phosphorus precursor can be but is not limited to one or more of tri (trimethyl silicon) phosphine, tri (triethyl silicon) phosphine, tri (diethyl amine) phosphine and tri (dimethyl amine) phosphine.
In some embodiments, the ratio of the amount of species of indium element in the first indium precursor to the amount of species of phosphorus element in the first phosphorus precursor is 1. Preferably, the ratio of the amount of the substance of the indium element in the first indium precursor to the amount of the substance of the phosphorus element in the first phosphorus precursor is 1. The ratio of the amount of indium element in the first indium precursor to the amount of zinc element in the first zinc precursor is 1. Preferably, the ratio of the amount of indium element in the first indium precursor to the amount of zinc element in the first zinc precursor is 1.
It is worth mentioning that after the step S1 is completed, the step S2 may be directly performed, or the step S2 may be performed after the first InZnP nucleus is purified and dispersed in a solvent.
In some embodiments, in the InZnP growth solution, the ratio of the amount of indium element in the second indium precursor to the amount of phosphorus element in the second phosphorus precursor is 1. The ratio of the amount of indium element in the second indium precursor to the amount of zinc element in the second zinc precursor is from 1 to 5.
In some embodiments, in the preparation method of the InZnP growth solution, the second reaction system reacts at 30-70 ℃ to obtain the InZnP growth solution containing InZnP clusters.
In some embodiments, the second indium precursor can be, but is not limited to, long chain acid indium, the second zinc precursor can be, but is not limited to, long chain zinc, and the second phosphorus precursor can be, but is not limited to, one or more of tris (trimethylsilylphosphine), tris (triethylsilylphosphine), tris (diethylamine) phosphine, tris (dimethylamine) phosphine.
In some embodiments, the second indium precursor and the second zinc precursor are prepared by: and mixing the indium precursor, the third ligand, the zinc precursor and the third non-coordinating solvent to form a third mixed solution. Preferably, the indium precursor, the third ligand, the zinc precursor and the third non-coordinating solvent are mixed, and the temperature is raised toReacting at 100-200 ℃ to form a third mixed solution. The third mixed solution includes a second indium precursor and a second zinc precursor. Wherein the indium precursor may be, but is not limited to, inCl 3 、In(MA) 3 、In(Ac) 3 One or more of (a). The zinc precursor can be, but is not limited to, zn (Ac) 2 、Zn(MA) 2 、Zn(St) 2 、Zn(OA) 2 One or more of (a).
In some embodiments, the second phosphorus precursor is prepared by: and mixing the phosphorus precursor, a fourth ligand and a fourth non-coordinating solvent to form a fourth mixed solution. The fourth mixed solution includes a second phosphorus precursor. Wherein, the phosphorus precursor can be but is not limited to one or more of tri (trimethyl silicon) phosphine, tri (triethyl silicon) phosphine, tri (diethyl amine) phosphine and tri (dimethyl amine) phosphine.
In each of the above embodiments, the first ligand, the second ligand, the third ligand, and the fourth ligand are each independently selected from one or more of fatty acid, amine ligand, and phosphine ligand; wherein the fatty acid is preferably one or more of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid and oleic acid; the amine ligand is preferably aliphatic amine, and further preferably the amine ligand is one or more of n-hexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine, dipropylamine and oleylamine; the phosphine ligand is preferably one or more of trioctylphosphine, tributylphosphine and trihexylphosphine.
In each of the above embodiments, the first non-coordinating solvent, the second non-coordinating solvent, the third non-coordinating solvent, and the fourth non-coordinating solvent are each independently selected from one or more of alkenes, alkanes, ethers, and aromatics.
In some embodiments, after step S2, step S3 is further included: at least one ZnSe is coated outside the nano crystal nucleus x S 1-x Wherein x is more than 0 and less than or equal to 1.
It is worth mentioning that after step S2 is completed, step S3 may be performed directly, or step S3 may be performed after the nanocrystal core is purified and dispersed in a solvent.
In some embodiments, after step S3, step S4 is further included: at ZnSe x S 1-x Outside the layerAnd coating a ZnS layer.
The invention also provides a quantum dot photoelectric device which comprises the cadmium-free quantum dot. The quantum dot optoelectronic device can be but is not limited to an OLED device, a QLED device, an LED device, a quantum dot laser, a quantum dot infrared light detector, a quantum dot single photon emission device and the like.
[ example 1 ]
Preparing an InZnP growth solution: 0.5mmol of In (Ac) 3 (indium acetate), 2mmol OA (oleic acid), 0.25mmol Zn (Ac) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 160 ℃ in an exhaust state, dissolving and cooling to 60 ℃; and (3) quickly injecting a mixed solution of 0.3mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.5mL of TOP and 0.5mL of ODE (octadecene), and reacting for 10min to obtain an InZnP growth solution. The amount of the growth liquid added can be adjusted according to the position of the quantum dot required to be synthesized.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) was weighed 3 (indium acetate), 0.2mmol of MA (tetradecanoic acid), 0.2mmol of Zn (Ac) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 290 ℃ and reacting for 2min to obtain a first InZnP nucleus, wherein a first exciton peak is 430nm;
(3) Dripping InZnP growth solution into the flask at 290 ℃, growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus, wherein the first exciton peak of the nanocrystal nucleus is 465nm;
(4) Se-TOP was added to the flask at 290 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 1mL of Se-TOP (0.1 mmol/mL) (selenium-trioctylphosphine) for reaction for 20min, adding 0.8mL of S-TOP (1 mmol/mL) (sulfur-trioctylphosphine) for reaction for 20min; cooling to room temperature after the reaction is finished, extracting for three times by using methanol, precipitating and centrifuging by using acetone, and dissolving the precipitate in toluene to obtain the InZnP/ZnSe/ZnS quantum dot solutionAnd carrying out absorption, emission and other performance tests.
[ example 2 ] A method for producing a polycarbonate
The preparation method of the InZnP growth solution was the same as that of the InZnP growth solution in example 1.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) was weighed 3 (indium acetate), 0.2mmol MA (tetradecanoic acid), 0.15mmol Zn (St) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 290 ℃ and reacting for 2min to obtain a first InZnP nucleus, wherein a first exciton peak is 433nm;
(3) Dripping InZnP growth solution into the flask at 290 ℃, and growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus; the first exciton peak is 470nm;
(4) Se-TOP was added to the flask at 290 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 1mL of Se-TOP (0.1 mmol/mL) (selenium-trioctylphosphine) for reaction for 20min, adding 0.8mL of S-TOP (1 mmol/mL) (sulfur-trioctylphosphine) for reaction for 20min; and after the reaction is finished, cooling to room temperature, extracting for three times by using methanol, precipitating and centrifuging by using acetone, dissolving the precipitate in toluene to obtain an InZnP/ZnSe/ZnS quantum dot solution, and carrying out absorption, emission and other performance tests.
[ example 3 ] A method for producing a polycarbonate
The preparation method of the InZnP growth solution is the same as that of the InZnP growth solution prepared in example 1.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) was weighed 3 (indium acetate), 0.2mmol MA (tetradecanoic acid), 0.15mmol Zn (St) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 270 ℃, and reacting for 2min to obtain a first InZnP nucleus with a first exciton peak of 428nm;
(3) And (3) dropwise adding the InZnP growth solution into the flask at 270 ℃, growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus, wherein the first exciton peak of the nanocrystal nucleus is 463nm.
(4) Se-TOP was added to the flask at 270 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 1mL of Se-TOP (0.1 mmol/mL) (selenium-trioctylphosphine) for reaction for 20min, adding 0.8mL of S-TOP (1 mmol/mL) (sulfur-trioctylphosphine) for reaction for 20min; and after the reaction is finished, cooling to room temperature, extracting for three times by using methanol, precipitating and centrifuging by using acetone, dissolving the precipitate in toluene to obtain an InZnP/ZnSe/ZnS quantum dot solution, and carrying out absorption, emission and other performance tests.
[ example 4 ]
The preparation method of the InZnP growth solution was the same as that of the InZnP growth solution in example 1.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) was weighed 3 (indium acetate), 0.2mmol of MA (tetradecanoic acid), 0.2mmol of Zn (Ac) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 290 ℃ and reacting for 2min to obtain a first InZnP nucleus, wherein a first exciton peak is 430nm;
(3) Dropwise adding the InZnP growth solution into a flask at 290 ℃, growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus, wherein the first exciton peak of the nanocrystal nucleus is 455nm;
(4) Se-TOP was added to the flask at 290 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 1mL of Se-TOP (0.1 mmol/mL) (selenium-trioctylphosphine) for reaction for 20min, then adding 0.5mL of dodecanethiol for reaction for 20min; cooling to room temperature after the reaction is finished, and adding methanolAnd extracting for three times, precipitating with acetone, centrifuging, dissolving the precipitate in toluene to obtain InZnP/ZnSe/ZnS quantum dot solution, and performing absorption, emission and other performance tests.
[ example 5 ]
Preparing an InZnP growth solution: 0.5mmol of In (Ac) 3 (indium acetate), 2mmol OA (oleic acid), 0.25mmol Zn (St) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 160 ℃ in an exhaust state, dissolving and cooling to room temperature; and quickly injecting a mixed solution of 0.3mmol TMS-P (tri (trimethylsilyl) phosphine), 0.5mL TOP and 0.5mL ODE (octadecene), and reacting for 10min to obtain an InZnP growth solution.
The cadmium-free quantum dot preparation method is the same as the cadmium-free quantum dot preparation method in example 1, except that the InZnP growth solution in step (3) is the InZnP growth solution prepared in this example. The first exciton peak to form the nanocrystal core was 460nm.
[ example 6 ] A method for producing a polycarbonate
Preparing an InZnP growth solution: 0.5mmol of In (Ac) was weighed 3 (indium acetate), 2mmol OA (oleic acid), 0.25mmol Zn (St) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 160 ℃ in an exhaust state, dissolving and cooling to 120 ℃; and quickly injecting a mixed solution of 0.3mmol TMS-P (tri (trimethylsilyl) phosphine), 0.5mL TOP and 0.5mL ODE (octadecene), and reacting for 10min to obtain an InZnP growth solution.
The preparation method of the cadmium-free quantum dot is the same as that of the cadmium-free quantum dot in example 1, except that the InZnP growth solution in step (3) is the InZnP growth solution prepared in this example. The first exciton peak to form the nanocrystal core was 475nm.
[ example 7 ]
The preparation method of the InZnP growth solution was the same as that of the InZnP growth solution in example 1.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) 3 (indium acetate), 0.2mmol of MA (tetradecanoic acid), 0.3mmol of Zn (Ac) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 290 ℃ and reacting for 2min to obtain a first InZnP nucleus of which the first exciton peak is 415nm;
(3) Dripping InZnP growth solution into the flask at 290 ℃, and growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus; the first exciton peak was 440nm.
(4) Se-TOP was added to the flask at 290 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 1mL of Se-TOP (0.1 mmol/mL) (selenium-trioctylphosphine) for reaction for 20min, adding 0.8mL of S-TOP (1 mmol/mL) (sulfur-trioctylphosphine) for reaction for 20min; and after the reaction is finished, cooling to room temperature, extracting for three times by using methanol, precipitating and centrifuging by using acetone, dissolving the precipitate in toluene to obtain an InZnP/ZnSe/ZnS quantum dot solution, and carrying out absorption, emission and other performance tests.
[ example 8 ]
The preparation method of the InZnP growth solution was the same as that of the InZnP growth solution in example 1.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) was weighed 3 (indium acetate), 0.2mmol of MA (tetradecanoic acid), 0.1mmol of Zn (Ac) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 290 ℃ and reacting for 2min to obtain a first InZnP nucleus, wherein a first exciton peak is 440nm;
(3) Dropwise adding an InZnP growth solution into the flask at 290 ℃, growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus, wherein the first exciton peak of the nanocrystal nucleus is 480nm;
(4) Se-TOP was added to the flask at 290 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (Zinc acetate), exhausting gas for 30min, heating to 280 deg.C, adding 1mL Se-TOP (0.1 mmol/mL) (Se-trioctylPhosphine), reacting for 20min, then adding 0.8mL S-TOP (1 mmol/mL) (sulfur-trioctylphosphine), and reacting for 20min; and after the reaction is finished, cooling to room temperature, extracting for three times by using methanol, precipitating and centrifuging by using acetone, dissolving the precipitate in toluene to obtain an InZnP/ZnSe/ZnS quantum dot solution, and carrying out absorption, emission and other performance tests.
[ example 9 ]
The preparation method of the InZnP growth solution was the same as that of the InZnP growth solution in example 1.
Preparing cadmium-free quantum dots:
(1) 0.1mmol of In (Ac) was weighed 3 (indium acetate), 0.2mmol of MA (tetradecanoic acid), 0.2mmol of Zn (Ac) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Heating to 180 ℃ in an exhaust state, dissolving and cooling to room temperature;
(2) Quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene) into a flask, heating to 290 ℃ and reacting for 2min to obtain a first InZnP nucleus, wherein a first exciton peak is 430nm;
(3) Dripping InZnP growth solution into the flask at 290 ℃, and growing a second InZnP nucleus outside the first InZnP nucleus to form a nanocrystal nucleus; the first exciton peak is 465nm;
(4) To the flask, se-TOP was added at 290 ℃ and then the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 0.8mL of Se-TOP (0.1 mmol/mL) (selenium-trioctylphosphine) and 0.2mL of S-TOP (0.1 mmol/mL) for reaction for 20min, adding 0.8mL of S-TOP (1 mmol/mL) (sulfur-trioctylphosphine) for reaction for 20min; cooling to room temperature after the reaction is finished, extracting for three times by using methanol, precipitating and centrifuging by using acetone, and dissolving the precipitate in toluene to obtain InZnP/ZnSe 0.8 S 0.2 the/ZnS quantum dot solution is used for carrying out absorption, emission and other performance tests.
Comparative example 1
Preparing cadmium-free quantum dots: 0.1mmol of In (Ac) 3 (indium acetate), 0.45mmol MA (tetradecanoic acid), 0.1mmol Zn (St) 2 5.0g ODE (octadecene) was charged in a 100mL three-necked flask, N 2 Exhaust stateHeating to 180 deg.c to dissolve and cool to room temperature; quickly injecting a mixed solution of 0.075mmol of TMS-P (tri (trimethylsilyl) phosphine), 0.2mL of TOP and 0.5mL of ODE (octadecene), and heating to 290 ℃ for reaction for 2min to obtain InZnP nuclei; se-TOP was added at 290 ℃ and the reaction temperature was lowered to 150 ℃ and 1.5mmol Zn (AC) was added 2 (zinc acetate), exhausting gas for 30min, heating to 280 ℃, adding 1ml of Se-TOP (0.1 mmol/ml) (selenium-trioctylphosphine) for reaction for 20min, then adding 0.8ml of S-TOP (1 mmol/ml) (sulfur-trioctylphosphine) for reaction for 20min; and after the reaction is finished, cooling to room temperature, extracting for three times by using methanol, precipitating and centrifuging by using acetone, dissolving the precipitate in toluene to obtain an InZnP/ZnSe/ZnS quantum dot solution, and carrying out absorption, emission and other performance tests.
The fluorescence emission spectrum instrument is adopted to test the fluorescence emission peak and half-peak width of the nuclear shell quantum dot, and the detection method of the quantum efficiency of the solution quantum dot comprises the following steps: the 450nm blue LED lamp is used as a light source, the spectrum of the blue light source and the spectrum after penetrating through the quantum dot solution are respectively tested by using the integrating sphere, and the quantum dot light efficiency is calculated by using the integral area of the spectrogram. Quantum efficiency = (quantum dot emission peak area)/(blue light source peak area-blue light source peak area not absorbed after passing through quantum dot solution) × 100%. The test results are shown in Table 1.
TABLE 1
Fluorescence emission peak/nm Half peak width/nm Quantum efficiency/%)
Comparative example 1 533 36 58.5％
Example 1 532 32 75.5％
Example 2 535 33 72.8％
Example 3 528 32 73.4％
Example 4 521 33 71.9％
Example 5 525 33 74.6％
Example 6 540 33 73.8％
Example 7 500 34 65.8％
Example 8 550 35 75.3％
Example 9 530 34 70.8％
As can be seen from the data in table 1: the half-peak width of the cadmium-free quantum dot prepared by the method is not more than 35nm, and the quantum efficiency is more than 60%; in comparative example 1, in which an InZnP core was prepared by a one-step method, the half-peak width was 36nm and the quantum efficiency was 58.5%. Therefore, the cadmium-free quantum dot prepared by the method is beneficial to reducing the half-peak width of the quantum dot and improving the quantum efficiency.
The quantum dot solutions of example 1 and comparative example 1 were used to fabricate quantum dot diaphragms, respectively, and the diaphragms were prepared by the same method: and (3) mixing the quantum dots with polyacrylate glue (wherein the quantum dots account for 3 wt%), coating the mixture on one barrier film, pasting the other barrier film, and carrying out ultraviolet curing. The fabricated membrane was subjected to various test conditions for a period of time, and then tested for quantum efficiency, the test conditions including: (1) irradiating at 70 ℃; (2) 65 ℃ and 95% relative humidity; (3) 85 ℃; and (4) 65 ℃. The test results are shown in fig. 1 and fig. 2, where fig. 1 shows the aging stability of the quantum dot membrane of example 1 under different conditions, and fig. 2 shows the aging stability of the quantum dot membrane of comparative example 1 under different conditions. The detection method of the quantum efficiency comprises the following steps: the 450nm blue LED lamp is used as a backlight spectrum, the integrating sphere is used for respectively testing the blue backlight spectrum and the spectrum penetrating through the quantum dot diaphragm, and the quantum dot luminous efficiency is calculated by using the integral area of a spectrogram. Quantum efficiency = (quantum dot emission peak area)/(blue backlight peak area-blue light peak area not absorbed through quantum dot film sheet) × 100%.
As can be seen from the data of fig. 1 and 2: the initial efficiency and stability of the membrane prepared by using the quantum dots of example 1 are remarkably improved compared with those of comparative example 1. Especially under the conditions of high temperature and high humidity (65 degrees/95%), the initial efficiency of the quantum dot diaphragm made of the quantum dots in the example 1 is 51.90%, and is reduced to 49.08% after 1056 hours, while the initial efficiency of the quantum dot diaphragm made of the quantum dots in the comparative example 1 is 45.05%, and is reduced to 39.77% after 1008 hours.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (16)

1. The cadmium-free quantum dot is characterized by comprising a nanocrystal core, wherein the nanocrystal core comprises a first InZnP core and a second InZnP core coated outside the first InZnP core, and the element proportions of the components of the first InZnP core and the second InZnP core are the same or different;
the shell comprises a ZnSexS1-x layer coated outside the nanocrystalline core, wherein x is more than 0 and less than or equal to 1, the fluorescence emission wavelength of the cadmium-free core-shell quantum dot is adjustable within the range of 500 to 550nm, the fluorescence half-peak width of the cadmium-free core-shell quantum dot is less than or equal to 35nm, and the quantum efficiency is more than or equal to 60%;
the shell layer also comprises a ZnS layer coated outside the ZnSexS1-x layer.
2. The cadmium-free quantum dot according to claim 1, wherein the first exciton peak position of the first InZnP core is adjustable within a range of 380-440nm.
3. A method for preparing a cadmium-free quantum dot, wherein the cadmium-free quantum dot comprises the cadmium-free quantum dot of claim 1, and the method comprises the following steps:
s1, preparing a solution containing a first InZnP nucleus;
s2, adding InZnP growth liquid containing InZnP clusters into the solution containing the first InZnP cores to grow second InZnP cores outside the first InZnP cores so as to obtain nanocrystal cores, wherein the InZnP growth liquid containing the InZnP clusters is prepared by the following method: and reacting a second reaction system comprising a second indium precursor, a second zinc precursor and a second phosphorus precursor at 25-150 ℃ to prepare the InZnP growth solution containing the InZnP cluster.
4. The method according to claim 3, wherein in step S1, a first reaction system comprising a first indium precursor, a first zinc precursor and a first phosphorus precursor is reacted at 150 to 330 ℃ to obtain the solution containing the first InZnP core.
5. The method for preparing the cadmium-free quantum dot according to claim 4, wherein the first reaction system is reacted at 180 to 300 ℃.
6. The method for preparing a cadmium-free quantum dot according to claim 4, wherein the ratio of the amount of the indium element in the first indium precursor to the amount of the phosphorus element in the first phosphorus precursor is 1.
7. The method for preparing the cadmium-free quantum dot according to claim 6, wherein the mass ratio of the indium element in the first indium precursor to the phosphorus element in the first phosphorus precursor is 1 to 1.
8. The method for preparing the cadmium-free quantum dot according to claim 4, wherein the mass ratio of the indium element in the first indium precursor to the zinc element in the first zinc precursor is 1 to 5-10.
9. The method for preparing a cadmium-free quantum dot according to claim 8, wherein the ratio of the amount of indium in the first indium precursor to the amount of zinc in the first zinc precursor is 1.
10. The method according to claim 3, wherein in the InZnP growth solution containing InZnP clusters, the ratio of the amounts of the indium element in the second indium precursor to the phosphorus element in the second phosphorus precursor is 1.
11. The method for preparing a cadmium-free quantum dot according to claim 10, wherein a ratio of the amount of the indium element in the second indium precursor to the amount of the phosphorus element in the second phosphorus precursor is 1 to 1.
12. The method for preparing a cadmium-free quantum dot according to claim 5, wherein the ratio of the amount of indium in the second indium precursor to the amount of zinc in the second zinc precursor is 1 to 5-10.
13. The method for preparing the cadmium-free quantum dot according to claim 12, wherein the mass ratio of the indium element in the second indium precursor to the zinc element in the second zinc precursor is 1 to 3-5.
14. The method for preparing cadmium-free quantum dots according to any one of claims 3 to 13, wherein after the step S2, the method further comprises a step S3: and at least one ZnSexS1-x layer is coated outside the nanocrystal core, wherein x is more than 0 and less than or equal to 1.
15. The method for preparing the cadmium-free quantum dot according to claim 14, wherein after the step S3, the method further comprises a step S4: and a ZnS layer is coated outside the ZnSexS1-x layer.
16. A quantum dot optoelectronic device comprising cadmium-free quantum dots according to any one of claims 1 to 2 or cadmium-free quantum dots produced by the production process according to any one of claims 3 to 15.
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