CN113755156B - Preparation method and application of PbSe/metal sulfide core-shell quantum dot - Google Patents
Preparation method and application of PbSe/metal sulfide core-shell quantum dot Download PDFInfo
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Abstract
The invention provides a preparation method and application of PbSe/metal sulfide core-shell quantum dots, wherein the method at least comprises the following steps: (1) obtaining an alcohol-soluble PbSe quantum dot nanomaterial; (2) Reacting a mixture containing an alcohol-soluble PbSe quantum dot nano material, a metal precursor and a polar solvent to obtain PbSe/metal sulfide core-shell quantum dots; the surface of the alcohol-soluble PbSe quantum dot nanomaterial contains a ligand, wherein the ligand comprises a sulfhydryl group; the metal precursor is at least one selected from cadmium metal precursor, zinc metal precursor and lead metal precursor. According to the preparation method provided by the invention, various PbSe/metal sulfide core-shell quantum dots with precisely controllable shell thickness can be successfully synthesized.
Description
Technical Field
The invention relates to the technical field of nano material synthesis, and relates to a preparation method and application of PbSe/metal sulfide core-shell quantum dots.
Background
PbSe quantum dots are important IV-VI semiconductor materials, and have the characteristics of narrow direct band gap (the band gap width of the bulk material is 0.28 eV), high dielectric constant, high carrier mobility and the like, and have the highest fluorescence quantum yield (approaching 90%) in all infrared semiconductor materials in the optical communication band (1300-1550 nm). Therefore, pbSe quantum dots have become a hot spot material for research and application. However, pbSe quantum dots are extremely susceptible to air oxidation, resulting in a decrease in their fluorescence quantum yield, thereby affecting the performance of their optoelectronic devices. To address the above issues, a shell coating strategy may be an ideal choice. In recent years, core-shell semiconductor quantum dots based on PbSe have been successfully prepared using a cation exchange method and an alternate ion layer adsorption growth method (SILAR). Unfortunately, the cation exchange process has the problem that it is difficult to precisely control the shell thickness, which is typically less than 2nm. The SILAR method has a disadvantage in that it requires a shell coating at a high temperature (200-350 ℃ C.) to easily cause aging of the PbSe core. Therefore, no report of synthesizing various PbSe-based core-shell quantum dots with precisely controllable shell thickness and widely tunable energy gaps in organic polar solvents has been made at present.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a preparation method of PbSe/metal sulfide core-shell quantum dots, which can successfully synthesize various PbSe/metal sulfide core-shell quantum dots with precisely controllable shell thickness.
In one aspect of the present application, a method for preparing a PbSe/metal sulfide core-shell quantum dot is provided, where the method at least includes:
(1) Obtaining an alcohol-soluble PbSe quantum dot nano material;
(2) Reacting a mixture containing an alcohol-soluble PbSe quantum dot nano material, a metal precursor and a polar solvent to obtain PbSe/metal sulfide core-shell quantum dots;
wherein, the surface ligand of the alcohol-soluble PbSe quantum dot nano material comprises sulfhydryl;
the metal precursor is at least one selected from cadmium metal precursor, zinc metal precursor and lead metal precursor.
Optionally, the metal precursor is selected from metal-soluble salts;
the metal soluble salt is at least one selected from metal nitrate, metal chloride, metal acetate, metal sulfate, metal carbonate and metal halide.
Optionally, the ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the mole number of the metal precursor is 10mg:10 -5 ～0.002mol；
Wherein the mole number of the metal precursor is calculated by the mole number of the metal element.
Optionally, the polar solvent is at least one selected from ethanol, methanol, ethylene glycol and dimethyl sulfoxide.
Alternatively, the conditions of reaction I are: the reaction temperature is 0-180 ℃; the reaction time is 1-50 min.
Alternatively, the upper temperature limit of reaction I is independently selected from 180 ℃, 150 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃; the lower limit is independently selected from 0 ℃, 150 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃.
Optionally, the upper time limit of reaction I is independently selected from 50min, 40min, 30min, 20min, 10min, 5min; the lower limit is independently selected from 1min, 40min, 30min, 20min, 10min, 5min.
Optionally, an organophosphine reagent is also included in the mixture; the organic phosphine reagent is at least one selected from tri-n-octyl phosphine, tri-n-butyl phosphine, diphenyl phosphine, triethyl phosphine, trimethoxy phosphine and tri-p-benzyl phosphine.
In the application, the PbSe quantum dot/metal sulfide composite nano material is easier to form by adding the organic phosphine reagent.
Optionally, the method at least comprises:
obtaining an alcohol-soluble PbSe quantum dot nano material;
(II) obtaining a first solution containing alcohol-soluble PbSe quantum dot nano material and a polar solvent;
(iii) obtaining a second solution comprising a metal precursor and a polar solvent;
and (IV) mixing the first solution and the second solution to obtain a mixture, and reacting I in an inactive atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot.
Preferably, the step (iv) comprises: and adding an organic phosphine reagent into the mixture, and reacting I in an inactive atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot.
Specifically, in the first solution, the mass ratio of the alcohol-soluble PbSe quantum dot nanomaterial to the polar solvent is not strictly required, and only the polar solvent is required to completely dissolve the alcohol-soluble PbSe quantum dot nanomaterial.
Preferably, in the first solution, the volume ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the polar solvent is 10mg: 1-6 mL.
Optionally, in the first solution, the upper limit of the volume ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the polar solvent is independently selected from 10mg:6mL, 10mg:5mL, 10mg:4mL, 10mg:3mL, 10mg:2mL; the lower limit is independently selected from 10mg:1mL, 10mg:5mL, 10mg:4mL, 10mg:3mL, 10mg:2mL.
Specifically, in the second solution, the mass ratio of the metal precursor to the polar solvent is not strictly required in the application, and only the polar solvent is required to completely dissolve the metal precursor.
Preferably, in the second solution, the volume ratio of the molar number of the metal precursor to the polar solvent is 10 -5 ～0.002mol：0.5～3mL。
Preferably, in the second solution, the volume ratio of the molar number of the metal precursor to the polar solvent is 10 -4 ～0.002mol：1mL。
Optionally, the second solution is prepared by the following method: and dissolving the metal precursor in 1-10 mL of polar solvent, and stirring under the protection of inert gas until the metal precursor is clear, thereby obtaining metal precursor solutions with different molar concentrations.
Preferably, the step (2) includes: mixing a solution containing an alcohol-soluble PbSe quantum dot nano material and a polar solvent with a solution containing a metal precursor and a polar solvent, adding an organic phosphine reagent, and reacting I to obtain the PbSe quantum dot/metal sulfide composite nano material.
Optionally, the step (2) includes: mixing a first solution containing an alcohol-soluble PbSe quantum dot nano material and a polar solvent with a second solution containing a metal precursor and a polar solvent, adding 0.1-2.0 mL of an organic phosphine reagent, controlling the reaction temperature to be 0-180 ℃ and the reaction time to be 1-50 min, and preparing the alcohol-soluble PbSe/metal sulfide core-shell quantum dot with the shell thickness accurately controllable (0.1-6.0 nm). The molar ratio of Pb ions to metal ions in the PbSe quantum dot nano material is 1:0.01-2, so that the prepared PbSe/metal sulfide core-shell quantum dot nano material can be ensured to have accurate shell thickness and energy gap capable of being tuned in a large range.
Optionally, the obtaining of the alcohol-soluble PbSe quantum dot nanomaterial at least comprises the following steps:
mixing an oil-soluble PbSe quantum dot nano material, a thiol compound and a polar solvent, and reacting III to obtain the alcohol-soluble PbSe quantum dot nano material.
Preferably, the conditions of reaction III are: the reaction temperature is 0-180 ℃; the reaction time is 5-50 min.
Optionally, the PbSe/metal sulfide core-shell quantum dot is an alcohol-soluble PbSe/metal sulfide core-shell quantum dot.
Alternatively, the upper temperature limit of reaction III is independently selected from 180 ℃, 150 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃; the lower limit is independently selected from 0 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃;150 ℃.
Optionally, the upper time limit of reaction III is independently selected from 50min, 40min, 30min, 20min, 10min; the lower limit is independently selected from 5min, 40min, 30min, 20min, 10min.
Optionally, the step (2) includes:
(2-1) reacting a mixture containing an alcohol-soluble PbSe quantum dot nano material, a metal precursor and a polar solvent to obtain an alcohol-soluble PbSe/metal sulfide core-shell quantum dot;
(2-2) mixing the alcohol-soluble PbSe/metal sulfide core-shell quantum dots with organic amine compounds and nonpolar solvents, and reacting II to obtain the PbSe/metal sulfide core-shell quantum dots; the PbSe/metal sulfide core-shell quantum dot is an oil-soluble PbSe/metal sulfide core-shell quantum dot.
Specifically, the preparation method for preparing the oil-soluble PbSe quantum dot/metal sulfide composite nanomaterial comprises the following steps:
(1) And separating out the quantum dots by using excessive toluene, centrifuging to obtain alcohol-soluble PbSe/metal sulfide quantum dot nano material precipitate, repeating the cleaning process to obtain high-purity alcohol-soluble PbSe/metal sulfide quantum dot nano material, and finally vacuum drying and grinding the quantum dot precipitate at 60 ℃ to obtain alcohol-soluble PbSe/metal sulfide quantum dot nano material powder.
(2) 10mg of alcohol-soluble PbSe/metal sulfide core-shell semiconductor quantum dot nano material powder, 0.1-3 mL of organic amine compound and 0.5-2 mL of nonpolar solvent are mixed and added into a three-neck flask, and continuously stirred to form suspension, the reaction temperature is controlled at 0-150 ℃ and the reaction time is controlled at 5-50 min, so that the reaction system is converted into clear and transparent solution from the original suspension, and at the moment, the alcohol-soluble PbSe/metal sulfide core-shell semiconductor quantum dot is converted into the oil-soluble PbSe/metal sulfide quantum dot. Adding excessive acetone into the reaction system to separate out alcohol-soluble PbSe/metal sulfide quantum dots, centrifuging to obtain oil-soluble PbSe/metal sulfide quantum dot precipitate, and finally vacuum drying and grinding the quantum dot material at 60 ℃ to obtain oil-soluble PbSe/metal sulfide quantum dot powder.
Optionally, in the step (2-2), the ratio between the mass of the alcohol-soluble PbSe/metal sulfide core-shell quantum dot, the volume of the organic amine compound and the volume of the nonpolar solvent is 10mg: 0.1-3 ml: 0.5-2 ml.
Preferably, the nonpolar solvent is selected from at least one of toluene, n-hexane, chloroform.
Alternatively, the conditions of reaction II are: the reaction temperature is 0-150 ℃; the reaction time is 5-50 min.
Optionally, the organic amine compound is at least one selected from octylamine, oleylamine, dodecylamine, octadecylamine and trioctylamine.
Alternatively, the upper temperature limit of reaction II is independently selected from 150 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃; the lower limit is independently selected from 0 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃.
Alternatively, the upper time limit of reaction II is independently selected from 50min, 40min, 30min, 20min, 10min; the lower limit is independently selected from 5min, 40min, 30min, 20min, 10min. In another aspect of the present application, there is also provided a PbSe/metal sulfide core-shell quantum dot selected from at least one of the PbSe/metal sulfide core-shell quantum dots prepared according to the above method.
Optionally, the PbSe/metal sulfide core-shell quantum dot is a core-shell structure of a metal sulfide coated PbSe quantum dot nano material;
wherein the core is PbSe quantum dot nano material, and the shell is metal sulfide.
Optionally, the thickness of the shell layer of the core-shell structure is 0.1-6.0 nm.
Alternatively, the upper shell thickness limit of the core-shell structure is independently selected from 6.0nm, 5.0nm, 4.0nm, 3.0nm, 2.0nm, 1.5nm, 1.0nm, 0.5nm; the lower limit is independently selected from 0.1nm;5.0nm, 4.0nm, 3.0nm, 2.0nm, 1.5nm, 1.0nm, 0.5nm.
On the other hand, the application also provides the PbSe/metal sulfide core-shell quantum dot prepared by the method and application of the PbSe/metal sulfide core-shell quantum dot in the photoelectric device field, the nano device field and the sensing field.
Optionally, the oil-soluble PbSe quantum dot nanomaterial is an oil-soluble PbSe quantum dot nanomaterial powder.
Optionally, the oil-soluble PbSe quantum dot nanomaterial powder is prepared by the following method: diluting the oil-soluble PbSe quantum dot prepared by the literature method with toluene, adding excessive acetone and methanol according to the ratio of 3:1 to precipitate the oil-soluble PbSe quantum dot nano material, centrifuging to obtain the precipitate of the oil-soluble PbSe quantum dot nano material, and repeating the cleaning process to obtain the high-purity oil-soluble PbSe quantum dot nano material. And finally, precipitating the oil-soluble PbSe quantum dot nano material, drying in vacuum at 60 ℃ and grinding to obtain oil-soluble PbSe quantum dot nano material powder.
Specifically, the method for obtaining the alcohol-soluble PbSe quantum dot nanomaterial at least comprises the following steps: 100mg of oil-soluble PbSe quantum dot nano material powder, 0.5-4 mL of thiol compound and 2-15 mL of polar solvent are mixed and added into a three-neck flask, and the mixture is continuously stirred to form suspension, the reaction temperature is controlled between 0 and 180 ℃ and the reaction time is controlled between 5 and 50 minutes, so that the reaction system is changed into clear and transparent solution from the original suspension, and at the moment, the oil-soluble PbSe quantum dot nano material is changed into alcohol-soluble PbSe quantum dot nano material. Adding excessive toluene into the reaction system to separate out alcohol-soluble quantum dots, centrifuging to obtain alcohol-soluble PbSe quantum dot nano material precipitate, and finally vacuum drying and grinding the nano material at 60 ℃ to obtain alcohol-soluble PbSe quantum dot nano material powder.
The oil-soluble PbSe quantum dot nanomaterial used in the embodiment of the application is prepared according to a literature (Nanotechnology, 2016,27,165202) method, and the oil-soluble PbSe quantum dot nanomaterial with the diameter of about 6nm is prepared.
The beneficial effects that this application can produce include:
1) The application provides a method for preparing PbSe/metal sulfide core-shell semiconductor quantum dots with universality, wherein the thickness of the shell layer is precisely controllable, and the energy gap can be tuned in a large range. The method can be used for successfully synthesizing PbSe/metal sulfide core-shell semiconductor quantum dots with various shell thicknesses accurately controllable (0.1-6.0 nm).
2) The method for preparing the PbSe/metal sulfide core-shell semiconductor quantum dot is simple in operation, mild in condition and applicable to multiple systems. The PbSe/metal sulfide core-shell semiconductor quantum dot with the precisely controllable shell thickness and the widely tunable energy gap is prepared by the method, and has wide application value in the fields of photoelectric devices, nano devices and sensing.
3) In the prior art, a cation exchange method and an alternate ion layer adsorption growth method (SILAR) are generally utilized to coat the PbSe quantum dots in a shell layer. In the cation exchange method, oil-soluble PbSe quantum dots are usually dissolved in a nonpolar solvent, and PbSe-based core-shell quantum dots are formed through ion exchange reaction. However, this method has a problem in that it is difficult to precisely control the thickness of the shell layer, which is generally less than 2nm. In addition, in the SILAR method, oil-soluble PbSe quantum dots are generally dispersed in a nonpolar solvent, and shell ions are alternately introduced at a high temperature to coat the PbSe quantum dots. However, this method generally requires a high reaction temperature (200-350 ℃) and thus is extremely susceptible to ripening of the oil-soluble PbSe quantum dot. In the application, the oil-soluble PbSe quantum dots are firstly treated into alcohol-soluble PbSe quantum dots, and then the alcohol-soluble PbSe quantum dots are dissolved in an organic polar solvent to carry out shell coating, such as ethanol, methanol, ethylene glycol or dimethyl sulfoxide, so that the temperature of the shell coating is reduced. By controlling the concentration of the metal precursor, quantitative metal precursor can be adsorbed on the surface of the PbSe quantum dot, the metal precursor and the mercapto alcohol compound are used as precursors of metal sulfide, and the PbSe/metal sulfide core-shell semiconductor quantum dot prepared at a certain reaction temperature has precise shell thickness and energy gap capable of being tuned in a large range.
4) In order to meet the requirements of photoelectric devices on quantum dots with different polarities, the application provides a method for converting an alcohol-soluble semiconductor nanomaterial into an oil-soluble semiconductor nanomaterial in a nonpolar solvent. The polar solvent is toluene, n-hexane, chloroform, etc.
Drawings
FIG. 1 is a transmission electron microscope image of an alcohol-soluble sample B2;
FIG. 2 is an absorption spectrum of alcohol-soluble PbSe/CdS core-shell quantum dots of samples B1-B5;
FIG. 3 is a fluorescence spectrum of alcohol-soluble PbSe/CdS core-shell quantum dots of samples B1-B5;
FIG. 4 is a transmission electron microscope image of an alcohol-soluble sample B8;
FIG. 5 is an absorption spectrum of alcohol-soluble PbSe/ZnS core-shell quantum dots of samples B6-B8;
FIG. 6 is a fluorescence spectrum of alcohol-soluble PbSe/ZnS core-shell quantum dots of samples B6-B8.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
In the application, a JEOL-JEM 2100F transmission electron microscope is adopted for TEM test, and the working potential is 200kV;
the absorption spectrum test adopts an Shimadzu UV-3600 ultraviolet visible near infrared spectrophotometer;
fluorescence spectroscopy testing used an FLS980 series steady state/transient fluorescence spectrometer.
The preparation method of the PbSe/metal sulfide core-shell quantum dot in the embodiment of the application comprises the following steps:
1) And dissolving the alcohol-soluble PbSe quantum dot nano material powder in a polar solvent, and stirring under the protection of inert gas until the mixture is clear to obtain an alcohol-soluble PbSe quantum dot nano material solution. The polar solvent environment is at least one of ethanol, methanol, glycol and dimethyl sulfoxide. The mass ratio of the alcohol-soluble PbSe quantum dot nano material to the polar solvent is 1:1 to 10.
2) And dissolving the metal precursor in 1-10 mL of polar solvent, and stirring under the protection of inert gas until the metal precursor is clear, thereby obtaining metal precursor solutions with different molar concentrations. Wherein the polar solvent environment is ethanol, methanol, ethylene glycol or dimethyl sulfoxide.
3) Mixing the solutions in the step 1) and the step 2), and adding 0.1-2.0 mL of organic phosphine reagent to obtain the alcohol-soluble PbSe/metal sulfide core-shell quantum dot.
The alcohol-soluble PbSe/metal sulfide core-shell quantum dot with accurate and controllable shell layer and large-range tunable energy gap can be prepared by optimizing metal ion types, metal ion concentration, reaction time, reaction temperature, selective use of an organic phosphine reagent and an organic polar solvent environment. The molar ratio of Pb ions to M metal ions in the PbSe quantum dots is 1:0.01-2; the reaction temperature is 0-180 ℃; the reaction time is 1-50 min; the organic phosphine reagent is tri-n-octyl phosphine or tri-n-butyl phosphine.
4) Blending alcohol-soluble PbSe/metal sulfide core-shell quantum dot powder, 1-10 mL of organic amine compound and 5-20 mL of nonpolar solvent, adding into a three-neck flask, continuously stirring to form suspension, controlling the reaction temperature to be 0-150 ℃ and the reaction time to be 5-50 min, and converting the original suspension into clear and transparent solution, wherein the alcohol-soluble PbSe/metal sulfide core-shell quantum dot is converted into the oil-soluble PbSe/metal sulfide quantum dot nanomaterial.
The alcohol-soluble PbSe quantum dot powder in the embodiment of the application is prepared by adopting the following method:
(1) Diluting 10g of oil-soluble PbSe quantum dots with 2mL of toluene, then adding 5mL of acetone and 5mL of methanol, separating out the oil-soluble PbSe quantum dots, centrifuging to obtain oil-soluble PbSe quantum dot precipitates, repeating the cleaning process to obtain high-purity oil-soluble PbSe quantum dots, and then vacuum drying and grinding the high-purity oil-soluble PbSe quantum dots at 60 ℃ to obtain oil-soluble PbSe quantum dot powder.
(2) 100mg of oil-soluble PbSe quantum dot powder, 10mL of mercaptohexanol and 100mL of polar solvent dimethyl sulfoxide are mixed and added into a three-neck flask, and the mixture is continuously stirred to form a suspension, the reaction temperature is controlled at 50 ℃ and the reaction time is controlled at 30min, so that the reaction system is changed into a clear and transparent solution from the original suspension, and at the moment, the oil-soluble PbSe quantum dots are changed into alcohol-soluble PbSe quantum dots. Adding excessive toluene into the reaction system to separate out alcohol-soluble PbSe quantum dots, centrifuging to obtain alcohol-soluble PbSe quantum dot precipitate, and finally vacuum drying and grinding the quantum dot material at 60 ℃ to obtain alcohol-soluble PbSe quantum dot powder.
Example 1 preparation of high quality PbSe/CdS core-shell Quantum dot composite nanomaterial
1) 10mg of alcohol-soluble PbSe quantum dot powder is dissolved in 3mL of ethanol, and the mixture is stirred under the protection of nitrogen until the mixture is clear, so as to obtain an alcohol-soluble PbSe quantum dot solution.
2) Cadmium nitrate is dissolved in 1mL of dimethyl sulfoxide, and stirred under the protection of nitrogen until the mixture is clear, so as to obtain cadmium nitrate solutions with different concentrations.
3) Mixing the solutions in the step 1) and the step 2), adding 0.1-2.0 mL of tri-n-butylphosphine which is an organic phosphine reagent, and controlling Pb in the PbSe quantum dots 2+ And Cd 2+ The molar ratio of the PbSe/CdS core-shell quantum dots is 1:0.01-2, the reaction time is 1-50 min, and the reaction temperature is 0-180 ℃, thus obtaining the alcohol-soluble PbSe/CdS core-shell quantum dots.
Preparation of oil-soluble PbSe/CdS core-shell semiconductor quantum dots: mixing 10mg of the alcohol-soluble PbSe/CdS core-shell semiconductor quantum dot powder obtained in the step 3), 0.1-3 mL of organic amine compound octylamine and 0.5-2 mL of toluene, adding into a three-neck flask, continuously stirring to form a suspension, controlling the reaction temperature to be 0-50 ℃ and the reaction time to be 5-50 min, and converting the original suspension into a clear and transparent solution, wherein the alcohol-soluble PbSe/CdS core-shell semiconductor quantum dot is converted into an oil-soluble PbSe/CdS quantum dot, so that the oil-soluble PbSe/CdS core-shell semiconductor quantum dot is obtained.
The concentration of the cadmium nitrate solution used in steps 1) to 3), the addition amount of the organophosphonic reagent, the time and the temperature of the reaction I are shown in Table 1.
TABLE 1
The conditions, reaction temperature and reaction time for preparing the oil-soluble PbSe/CdS core-shell semiconductor quantum dots are shown in Table 2.
TABLE 2
Example 2 preparation of high quality PbSe/ZnS core-shell semiconductor Quantum dots
The metal precursor solution used in this example was zinc nitrate solution, and the other synthesis steps were the same as in example 1. The reaction conditions for preparing the alcohol-soluble PbSe/ZnS core-shell quantum dots are shown in Table 3. The reaction conditions for the preparation of the oil-soluble PbSe/ZnS core-shell quantum dots are shown in Table 4.
The concentration of the zinc nitrate solution used in steps 1) to 3), the addition amount of the organophosphonic reagent, the time and the temperature of the reaction I are shown in Table 3.
TABLE 3 Table 3
The conditions, reaction temperature and reaction time for preparing the oil-soluble PbSe/ZnS core-shell semiconductor quantum dots are shown in Table 4.
TABLE 4 Table 4
Example 3 characterization of morphology of PbSe/Metal sulfide core-shell semiconductor Quantum dots
The samples B1-B5 and M1-M5 are subjected to morphology characterization by using a JEOL-JEM 2100F transmission electron microscope, the typical representation is shown in a graph in figure 1, the graph in figure 1 shows a transmission electron microscope diagram of PbSe/CdS core-shell quantum dots of the sample B2, the total diameter of the PbSe/CdS core-shell quantum dots is 6.5nm, the thickness of a shell layer is 1-1.5nm, and the prepared quantum dot material has high uniformity in size.
The samples B6-B8 and M6-M8 are subjected to morphology characterization by using a JEOL-JEM 2100F transmission electron microscope, and a typical transmission electron microscope diagram of the PbSe/ZnS core-shell quantum dot of the sample B8 is shown in FIG. 4, and the transmission electron microscope diagram of the PbSe/ZnS core-shell quantum dot of the sample B8 shows that the total diameter of the PbSe/ZnS core-shell quantum dot is 9.5nm, the thickness of a shell layer is 2-4nm, and the prepared quantum dot material has high size uniformity.
Example 4 absorption Spectrometry testing of PbSe/Metal sulfide core-shell semiconductor Quantum dots
The samples B1-B5 and M1-M5 were subjected to absorption spectrum test by using an Shimadzu UV-3600 ultraviolet visible near infrared spectrophotometer, and represented by the samples B1-B5, and FIG. 2 shows the absorption spectrum diagrams of PbSe/CdS core-shell quantum dots of the samples B1-B5, and it can be seen from the diagrams that the absorption peaks of the quantum dots from left to right are 1470nm (corresponding to sample B1), 1510nm (corresponding to sample B2), 1590nm (corresponding to sample B3), 1655nm (corresponding to sample B4) and 1750nm (corresponding to sample B5), respectively.
The absorption spectrum test is carried out on samples B6-B8 and M6-M8 by using an Shimadzu UV-3600 ultraviolet visible near infrared spectrophotometer, the absorption spectrum of PbSe/ZnS core-shell quantum dots of the samples B6-B8 is represented by the samples B6-B8, and the absorption peaks of the quantum dots from left to right are 1480nm (corresponding to the sample B6) and 1520nm (corresponding to the sample B7) to 1560nm (corresponding to the sample B8) respectively.
Example 5 fluorescence Spectrum testing of PbSe/Metal sulfide core-shell semiconductor Quantum dots
Samples B1-B5 and M1-M5 were subjected to fluorescence spectrum testing by using FLS980 series steady state/transient state fluorescence spectrometer, and represented by samples B1-B5, and FIG. 3 shows the fluorescence spectrum of PbSe/CdS core-shell quantum dots of samples B1-B5, and the fluorescence peaks of the quantum dots from left to right are 1512nm (corresponding to sample B1), 1555nm (corresponding to sample B2), 1620nm (corresponding to sample B3), 1688nm (corresponding to sample B4) and 1790nm (corresponding to sample B5), respectively.
Samples B6-B8 and M6-M8 were subjected to fluorescence spectrum testing by using FLS980 series steady state/transient state fluorescence spectrometer, and represented by sample B6-B8, and FIG. 6 shows the fluorescence spectrum diagram of PbSe/ZnS core-shell quantum dots of sample B6-B8, and the absorption peaks of the quantum dots from left to right are 1510nm (corresponding to sample B6), 1560nm (corresponding to sample B7) to 1600nm (corresponding to sample B8), respectively.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (20)
1. The preparation method of the PbSe/metal sulfide core-shell quantum dot is characterized by at least comprising the following steps:
(1) Obtaining an alcohol-soluble PbSe quantum dot nano material;
(2) Reacting a mixture containing an alcohol-soluble PbSe quantum dot nano material, a metal precursor and a polar solvent to obtain PbSe/metal sulfide core-shell quantum dots;
the surface of the alcohol-soluble PbSe quantum dot nanomaterial contains a ligand, wherein the ligand comprises a sulfhydryl group;
the metal precursor is at least one selected from cadmium metal precursor, zinc metal precursor and lead metal precursor.
2. The method of preparation of claim 1, wherein the metal precursor is selected from the group consisting of metal soluble salts;
the metal soluble salt is at least one selected from metal nitrate, metal chloride, metal acetate, metal sulfate, metal carbonate and metal halide.
3. The preparation method according to claim 1, wherein the ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the number of moles of metal precursor is 10mg:10 -5 ～0.002mol；
Wherein the mole number of the metal precursor is calculated by the mole number of the metal element.
4. The method according to claim 1, wherein the polar solvent is at least one selected from the group consisting of ethanol, methanol, ethylene glycol, and dimethyl sulfoxide.
5. The process of claim 1, wherein the conditions for reaction I are: the reaction temperature is 0-180 ℃; the reaction time is 1-50 min.
6. The method of claim 1, wherein the mixture further comprises an organophosphine reagent; the organic phosphine reagent is at least one selected from tri-n-octyl phosphine, tri-n-butyl phosphine, diphenyl phosphine, triethyl phosphine, trimethoxy phosphine and tri-p-benzyl phosphine.
7. The method according to claim 1, characterized in that it comprises at least:
obtaining an alcohol-soluble PbSe quantum dot nano material;
(II) obtaining a first solution containing alcohol-soluble PbSe quantum dot nano material and a polar solvent;
(iii) obtaining a second solution comprising a metal precursor and a polar solvent;
and (IV) mixing the first solution and the second solution to obtain a mixture, and reacting I in an inactive atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot.
8. The method of claim 7, wherein step (iv) comprises: and adding an organic phosphine reagent into the mixture, and reacting I in an inactive atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot.
9. The method of claim 7, wherein in the first solution, the volume ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the polar solvent is 10mg: 1-6 mL.
10. The method according to claim 7, wherein the volume ratio of the number of moles of the metal precursor to the polar solvent in the second solution is 10 -5 ～0.002mol：0.5～3mL。
11. The preparation method of claim 8, wherein the obtaining of the alcohol-soluble PbSe quantum dot nanomaterial comprises at least the following steps:
mixing an oil-soluble PbSe quantum dot nano material, a thiol compound and a polar solvent, and reacting III to obtain the alcohol-soluble PbSe quantum dot nano material.
12. The method of claim 11, wherein the conditions for reaction III are: the reaction temperature is 0-180 ℃; the reaction time is 5-50 min.
13. The preparation method of claim 1, wherein the PbSe/metal sulfide core-shell quantum dots obtained in the step (2) are alcohol-soluble PbSe/metal sulfide core-shell quantum dots.
14. The method of claim 1, wherein step (2) comprises:
(2-1) reacting a mixture containing an alcohol-soluble PbSe quantum dot nano material, a metal precursor and a polar solvent to obtain an alcohol-soluble PbSe/metal sulfide core-shell quantum dot;
(2-2) mixing the alcohol-soluble PbSe/metal sulfide core-shell quantum dots with organic amine compounds and nonpolar solvents, and reacting II to obtain the PbSe/metal sulfide core-shell quantum dots; the PbSe/metal sulfide core-shell quantum dot is an oil-soluble PbSe/metal sulfide core-shell quantum dot.
15. The method according to claim 14, wherein in the step (2-2), the ratio of the mass of the alcohol-soluble PbSe/metal sulfide core-shell quantum dot, the volume of the organic amine compound, and the volume of the nonpolar solvent is 10mg: 0.1-3 ml: 0.5-2 ml.
16. The method according to claim 14, wherein the nonpolar solvent is at least one selected from toluene, n-hexane, and chloroform.
17. The process of claim 14, wherein the conditions for reaction II are: the reaction temperature is 0-150 ℃; the reaction time is 5-50 min.
18. The method according to claim 14, wherein the organic amine compound is at least one selected from octylamine, oleylamine, dodecylamine, octadecylamine, trioctylamine.
19. The preparation method of claim 1, wherein the PbSe/metal sulfide core-shell quantum dots are of a core-shell structure of metal sulfide coated PbSe quantum dot nanomaterial;
wherein the core is PbSe quantum dot nano material, and the shell is metal sulfide.
20. The method according to claim 1, wherein the shell layer thickness of the core-shell structure is 0.1 to 6.0nm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250403A (en) * | 2008-02-28 | 2008-08-27 | 上海交通大学 | Method for synthesizing water-soluble long-chain mercapto compound coated cadmium telluride quantum dot |
| CN103965907A (en) * | 2013-01-29 | 2014-08-06 | 华东理工大学 | Near-infrared fluorescence emitting CdTe/CdS core/shell quantum dot, and preparation method thereof |
| CN104650848A (en) * | 2014-04-24 | 2015-05-27 | 陈续晋 | Preparation method for high-stability quantum dot composite |
| CN104692340A (en) * | 2014-07-28 | 2015-06-10 | 深圳丹邦投资集团有限公司 | Selenium precursor for preparing metal selenide nanometer material |
| CN106848079A (en) * | 2017-02-20 | 2017-06-13 | 纳晶科技股份有限公司 | Luminous electric charge transmission compound, the ink containing it, its preparation method and QLED devices |
| CN109980102A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | Luminescent material and preparation method thereof and QLED device |
-
2020
- 2020-06-03 CN CN202010495257.4A patent/CN113755156B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250403A (en) * | 2008-02-28 | 2008-08-27 | 上海交通大学 | Method for synthesizing water-soluble long-chain mercapto compound coated cadmium telluride quantum dot |
| CN103965907A (en) * | 2013-01-29 | 2014-08-06 | 华东理工大学 | Near-infrared fluorescence emitting CdTe/CdS core/shell quantum dot, and preparation method thereof |
| CN104650848A (en) * | 2014-04-24 | 2015-05-27 | 陈续晋 | Preparation method for high-stability quantum dot composite |
| CN104692340A (en) * | 2014-07-28 | 2015-06-10 | 深圳丹邦投资集团有限公司 | Selenium precursor for preparing metal selenide nanometer material |
| CN106848079A (en) * | 2017-02-20 | 2017-06-13 | 纳晶科技股份有限公司 | Luminous electric charge transmission compound, the ink containing it, its preparation method and QLED devices |
| CN109980102A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | Luminescent material and preparation method thereof and QLED device |
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