CN113755156A - 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 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 of the alcohol-soluble PbSe quantum dot nano material contains a ligand, and the ligand comprises sulfydryl; the metal precursor is at least one of cadmium metal precursor, zinc metal precursor and lead metal precursor. According to the preparation method, PbSe/metal sulfide core-shell quantum dots with various shell thicknesses which are accurately controllable can be successfully synthesized.
Description
Technical Field
The invention relates to the technical field of nano material synthesis, in particular to a preparation method and application of PbSe/metal sulfide core-shell quantum dots.
Background
As an important IV-VI semiconductor material, PbSe quantum dot not only has the characteristics of narrow direct band gap (the band gap width of a bulk material is 0.28eV), high dielectric constant, high carrier mobility and the like, but also has the highest fluorescence quantum yield (close to 90%) in all infrared semiconductor materials in the optical communication wave band (1300-1550 nm). Thus, PbSe quantum dots have become a hot material for research and application. However, PbSe quantum dots are very susceptible to air oxidation, resulting in a decrease in the fluorescence quantum yield thereof, thereby affecting the performance of the optoelectronic device thereof. To solve the above problem, a shell coating strategy may be an ideal choice. In recent years, PbSe-based core-shell semiconductor quantum dots have been successfully prepared by a cation exchange method and an alternate ion-layer adsorption growth method (SILAR). Unfortunately, cation exchange methods suffer from the difficulty of precisely controlling the shell thickness, which is typically less than 2 nm. The SILAR method has a disadvantage that the PbSe core is easily cured because the shell coating is required at a high temperature (200 ℃ C. and 350 ℃ C.). Therefore, no report exists at present for universally synthesizing various PbSe-based core-shell quantum dots with accurately controllable shell thicknesses and widely tunable energy gaps in organic polar solvents.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a preparation method of the PbSe/metal sulfide core-shell quantum dot, which can successfully synthesize the PbSe/metal sulfide core-shell quantum dot with various shell thicknesses which are accurately controllable.
In one aspect of the present application, a method for preparing PbSe/metal sulfide core-shell quantum dots is provided, the method at least comprising:
(1) obtaining 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 sulfydryl;
the metal precursor is at least one of 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 nano material to the mole number of the metal precursor is 10mg:10-5～0.002mol；
Wherein the number of moles of the metal precursor is based on the number of moles of the metal element.
Optionally, the polar solvent is selected from at least one of ethanol, methanol, ethylene glycol, dimethyl sulfoxide.
Optionally, the conditions of reaction I are: the reaction temperature is 0-180 ℃; the reaction time is 1-50 min.
Optionally, the upper temperature limit of reaction I is independently selected from 180 ℃, 150 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃; the lower limit is independently selected from the group consisting of 0 deg.C, 150 deg.C, 100 deg.C, 80 deg.C, 50 deg.C, and 30 deg.C.
Optionally, the upper time limit of reaction I is independently selected from 50min, 40min, 30min, 20min, 10min, 5 min; the lower limit is independently selected from 1min, 40min, 30min, 20min, 10min, 5 min.
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-phenyl methyl 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 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;
(IV) mixing the first solution and the second solution to obtain the mixture, and reacting the mixture I in an inert atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot.
Preferably, the step (iv) includes: and adding an organic phosphine reagent into the mixture, and reacting 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 the alcohol-soluble PbSe quantum dot nanomaterial is completely dissolved by the polar solvent.
Preferably, in the first solution, the ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the volume of the polar solvent is 10mg: 1-6 mL.
Optionally, in the first solution, the upper limit of the ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the volume of the polar solvent is independently selected from 10mg: 6mL, 10mg: 5mL, 10mg: 4mL, 10mg: 3mL, 10mg: 2 mL; the lower limit is independently selected from 10mg: 1mL, 10mg: 5mL, 10mg: 4mL, 10mg: 3mL, 10mg: 2 mL.
Specifically, in the second solution, the mass ratio of the metal precursor to the polar solvent is not strictly required in the present application, and the metal precursor is completely dissolved by the polar solvent.
Preferably, in the second solution, the ratio of the number of moles of the metal precursor to the volume of the polar solvent is 10-5～0.002mol：0.5～3mL。
Preferably, in the second solution, the ratio of the number of moles of the metal precursor to the volume of the polar solvent is 10-4～0.002mol：1mL。
Optionally, the second solution is prepared by the following method: dissolving a metal precursor in 1-10 mL of polar solvent, and stirring the solution to be clear under the protection of inert gas to obtain metal precursor solutions with different molar concentrations.
Preferably, the step (2) includes: and (2) mixing the solution containing the alcohol-soluble PbSe quantum dot nano material and the polar solvent with the solution containing the metal precursor and the 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) comprises: 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 the polar solvent, adding 0.1-2.0 mL of an organic phosphine reagent, controlling the reaction temperature at 0-180 ℃ and the reaction time at 1-50 min, and preparing the alcohol-soluble PbSe/metal sulfide core-shell quantum dot with the accurate and controllable shell layer thickness (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 nuclear shell quantum dot nano material has accurate shell thickness and large-range tunable energy gap.
Optionally, the obtaining of the alcohol-soluble PbSe quantum dot nanomaterial at least comprises the following steps:
and mixing the oil-soluble PbSe quantum dot nano material, a thiol alcohol compound and a polar solvent, and reacting III to obtain the alcohol-soluble PbSe quantum dot nano material.
Preferably, the conditions of the 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.
Optionally, 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 deg.C, 100 deg.C, 80 deg.C, 50 deg.C, 30 deg.C; at 150 ℃.
Optionally, the upper time limit of reaction III is independently selected from 50min, 40min, 30min, 20min, 10 min; the lower limit is independently selected from 5min, 40min, 30min, 20min, 10 min.
Optionally, the step (2) comprises:
(2-1) reacting the mixture containing the alcohol-soluble PbSe quantum dot nano material, the metal precursor and the polar solvent to obtain alcohol-soluble PbSe/metal sulfide core-shell quantum dots;
(2-2) mixing the alcohol-soluble PbSe/metal sulfide nuclear shell quantum dots with an organic amine compound and a nonpolar solvent, and reacting II to obtain the PbSe/metal sulfide nuclear shell quantum dots; the PbSe/metal sulfide nuclear shell quantum dots are oil-soluble PbSe/metal sulfide nuclear shell quantum dots.
Specifically, the preparation method for preparing the oil-soluble PbSe quantum dot/metal sulfide composite nano material comprises the following steps:
(1) separating out the quantum dots from the prepared alcohol-soluble PbSe/metal sulfide nuclear shell semiconductor quantum dot nano material by using excessive toluene, centrifuging to obtain alcohol-soluble PbSe/metal sulfide quantum dot nano material precipitate, repeating the cleaning process to obtain the high-purity alcohol-soluble PbSe/metal sulfide quantum dot nano material, and finally drying and grinding the alcohol-soluble PbSe/metal sulfide quantum dot nano material precipitate in vacuum at the temperature of 60 ℃ to obtain the alcohol-soluble PbSe/metal sulfide quantum dot nano material powder.
(2) 10mg of alcohol-soluble PbSe/metal sulfide nuclear 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 to be 0-150 ℃ and the reaction time is controlled to be 5-50 min, so that the original suspension of a reaction system is converted into clear and transparent solution, and the alcohol-soluble PbSe/metal sulfide nuclear shell semiconductor quantum dot is converted into 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 precipitates, and finally, drying the quantum dot materials at 60 ℃ in vacuum and grinding to obtain oil-soluble PbSe/metal sulfide quantum dot powder.
Optionally, in the step (2-2), the ratio of the mass of the alcohol-soluble PbSe/metal sulfide core-shell quantum dots, 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, and 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.
Optionally, the upper temperature limit of reaction II is independently selected from 150 ℃, 100 ℃, 80 ℃, 50 ℃, 30 ℃; the lower limit is independently selected from the group consisting of 0 deg.C, 100 deg.C, 80 deg.C, 50 deg.C, and 30 deg.C.
Optionally, the upper time limit of reaction II is independently selected from 50min, 40min, 30min, 20min, 10 min; the lower limit is independently selected from 5min, 40min, 30min, 20min, 10 min. In another aspect of the present application, there is also provided a PbSe/metal sulfide core-shell quantum dot, wherein the PbSe/metal sulfide core-shell quantum dot is 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 nanomaterial;
wherein, the core is a PbSe quantum dot nano material, and the shell is a metal sulfide.
Optionally, the thickness of the shell layer of the core-shell structure is 0.1-6.0 nm.
Optionally, the upper limit of the shell thickness of the core-shell structure is independently selected from 6.0nm, 5.0nm, 4.0nm, 3.0nm, 2.0nm, 1.5nm, 1.0nm, 0.5 nm; the lower limit is independently selected from 0.1 nm; 5.0nm, 4.0nm, 3.0nm, 2.0nm, 1.5nm, 1.0nm, 0.5 nm.
On the other hand, the application also provides the PbSe/metal sulfide nuclear shell quantum dot prepared by the method and the application of the PbSe/metal sulfide nuclear shell quantum dot in the fields of photoelectric devices, nano devices and sensing.
Optionally, the oil-soluble PbSe quantum dot nanomaterial is 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 dots prepared according to a literature method with toluene, adding excessive acetone and methanol according to the proportion of 3:1 to separate out the oil-soluble PbSe quantum dot nano material, centrifuging to obtain oil-soluble PbSe quantum dot nano material precipitate, and repeating the cleaning process to obtain the high-purity oil-soluble PbSe quantum dot nano material. And finally, carrying out vacuum drying on the oil-soluble PbSe quantum dot nano material precipitate at 60 ℃ and grinding to obtain oil-soluble PbSe quantum dot nano material powder.
Specifically, the obtaining of the alcohol-soluble PbSe quantum dot nano material at least comprises the following steps: 100mg of oil-soluble PbSe quantum dot nano material powder, 0.5-4 mL of thiol alcohol compound and 2-15 mL of polar solvent are blended and added into a three-neck flask and continuously stirred to form suspension, the reaction temperature is controlled to be 0-180 ℃ and the reaction time is controlled to be 5-50 min, so that the reaction system is converted into clear and transparent solution from the original suspension, and at the moment, the oil-soluble PbSe quantum dot nano material is converted into the 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, drying the nano material at 60 ℃ in vacuum and grinding to obtain alcohol-soluble PbSe quantum dot nano material powder.
The oil-soluble PbSe quantum dot nanomaterial used in the examples of the present application was prepared according to a literature (Nanotechnology,2016,27,165202) method to prepare an oil-soluble PbSe quantum dot nanomaterial with a diameter of about 6 nm.
The beneficial effects that this application can produce include:
1) the application provides a universal method for preparing PbSe/metal sulfide nuclear shell semiconductor quantum dots with accurately controllable shell thickness and large-range tunable energy gap. The method can successfully synthesize a plurality of PbSe/metal sulfide nuclear shell semiconductor quantum dots with accurately controllable shell thicknesses (0.1-6.0 nm).
2) The method for preparing the PbSe/metal sulfide core-shell semiconductor quantum dots is simple to operate, mild in condition and applicable to multiple systems. The PbSe/metal sulfide nuclear shell semiconductor quantum dot which is prepared by the method and has the advantages of accurate and controllable shell layer thickness and large-range tunable energy gap has wide application value in the fields of photoelectric devices, nano devices and sensing.
3) In the prior art, PbSe quantum dots are generally coated with shells by a cation exchange method and an alternate ion layer adsorption growth method (SILAR). Among them, the cation exchange method is generally to dissolve oil-soluble PbSe quantum dots in a non-polar solvent and form PbSe-based core-shell quantum dots through an ion exchange reaction. However, this method has a problem that it is difficult to precisely control the thickness of the shell layer, which is generally less than 2 nm. In addition, the SILAR method generally includes dispersing oil-soluble PbSe quantum dots in a nonpolar solvent, and shell-coating the PbSe quantum dots by alternately introducing shell ions at a high temperature. However, this method generally requires high reaction temperatures (200-. In the present application, the oil-soluble PbSe quantum dots are first processed into alcohol-soluble PbSe quantum dots, and then the alcohol-soluble PbSe quantum dots are dissolved in an organic polar solvent to perform shell coating, such as ethanol, methanol, ethylene glycol or dimethyl sulfoxide, so as to reduce the temperature of the shell coating. By controlling the concentration of the metal precursor, a quantitative metal precursor can be adsorbed on the surface of the PbSe quantum dot, the metal precursor and the thiol alcohol compound are used as precursors of metal sulfides, and the PbSe/metal sulfide core-shell semiconductor quantum dot prepared at a certain reaction temperature has accurate shell thickness and large-range tunable energy gap.
4) In order to meet the requirements of photoelectric devices on quantum dots with different polarities, the application provides a method for converting alcohol-soluble semiconductor nano materials into oil-soluble semiconductor nano materials in a non-polar solvent. The polar solvent is toluene, n-hexane, chloroform, etc.
Drawings
FIG. 1 is a transmission electron micrograph of an alcohol-soluble sample B2;
FIG. 2 is a absorption spectrum of alcohol-soluble PbSe/CdS core-shell quantum dots of sample B1-B5;
FIG. 3 is a fluorescence spectrum of alcohol-soluble PbSe/CdS core-shell quantum dots of sample B1-B5;
FIG. 4 is a transmission electron micrograph of alcohol soluble sample B8;
FIG. 5 is an absorption spectrum of alcohol-soluble PbSe/ZnS core-shell quantum dots of sample 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 will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the application, a JEOL-JEM 2100F transmission electron microscope is adopted for TEM test, and the working potential is 200 kV;
the absorption spectrum test adopts an Shimadzu UV-3600 ultraviolet visible near-infrared spectrophotometer;
fluorescence spectroscopy was performed using 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) dissolving alcohol-soluble PbSe quantum dot nano material powder in a polar solvent, and stirring the solution to be clear under the protection of inert gas to obtain an alcohol-soluble PbSe quantum dot nano material solution. The polar solvent environment is at least one of ethanol, methanol, ethylene 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) Dissolving a metal precursor in 1-10 mL of polar solvent, and stirring the solution to be clear under the protection of inert gas to obtain metal precursor solutions with different molar concentrations. Wherein the polar solvent environment is ethanol, methanol, ethylene glycol or dimethyl sulfoxide.
3) And (3) mixing the solutions obtained 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.
By optimizing the metal ion type, the metal ion concentration, the reaction time, the reaction temperature, the selective use of an organic phosphine reagent and the organic polar solvent environment of the system, the alcohol-soluble PbSe/metal sulfide core-shell quantum dot with a precisely controllable shell layer and a large-range tunable energy gap can be prepared. 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 nuclear shell quantum dot powder, 1-10 mL of organic amine compound and 5-20 mL of nonpolar solvent, adding the mixture into a three-neck flask, continuously stirring to obtain a suspension, controlling the reaction temperature to be 0-150 ℃ and the reaction time to be 5-50 min, converting the original suspension into a clear and transparent solution, and converting the alcohol-soluble PbSe/metal sulfide nuclear shell quantum dot into an oil-soluble PbSe/metal sulfide quantum dot nano material.
The alcohol-soluble PbSe quantum dot powder in the embodiment of the application is prepared by the following method:
(1) diluting 10g of oil-soluble PbSe quantum dots by using 2mL of methylbenzene, 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 drying and grinding the high-purity oil-soluble PbSe quantum dots in vacuum 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 blended and added into a three-neck flask and continuously stirred to form suspension, the reaction temperature is controlled at 50 ℃ and the reaction time is controlled for 30min, so that the reaction system is changed from the original suspension into a clear and transparent solution, and at the moment, the oil-soluble PbSe quantum dot is changed into the alcohol-soluble PbSe quantum dot. Adding excessive toluene into the reaction system to separate out alcohol-soluble PbSe quantum dots, centrifuging to obtain alcohol-soluble PbSe quantum dot precipitates, and finally, drying the quantum dot material at 60 ℃ in vacuum and grinding to obtain alcohol-soluble PbSe quantum dot powder.
Example 1 preparation of high quality PbSe/CdS core-shell quantum dot composite nanomaterial
1) Dissolving 10mg of alcohol-soluble PbSe quantum dot powder in 3mL of ethanol, and stirring the solution under the protection of nitrogen until the solution is clear to obtain an alcohol-soluble PbSe quantum dot solution.
2) Cadmium nitrate is dissolved in 1mL of dimethyl sulfoxide, and the solution is stirred to be clear under the protection of nitrogen, so that cadmium nitrate solutions with different concentrations are obtained.
3) Mixing the solutions obtained in the step 1) and the step 2), adding 0.1-2.0 mL of organic phosphine reagent tri-n-butylphosphine, and controlling Pb in the PbSe quantum dots2+And Cd2+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 ℃, so that the alcohol-soluble PbSe/CdS core-shell quantum dots can be obtained.
Preparing oil-soluble PbSe/CdS core-shell semiconductor quantum dots: blending 10mg of 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 methylbenzene, adding the mixture into a three-neck flask, continuously stirring to obtain a suspension, controlling the reaction temperature to be 0-50 ℃ and the reaction time to be 5-50 min, converting the original suspension into a clear and transparent solution, and converting the alcohol-soluble PbSe/CdS core-shell semiconductor quantum dot into an oil-soluble PbSe/CdS quantum dot to obtain the oil-soluble PbSe/CdS core-shell semiconductor quantum dot.
The concentration of the cadmium nitrate solution used in steps 1) to 3), the amount of organophosphine reagent added, the time and temperature of reaction I are shown in Table 1.
TABLE 1
The conditions, reaction temperature and 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 a 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 preparing 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 amount of organophosphine reagent added, the time and temperature of reaction I are shown in Table 3.
TABLE 3
The conditions, reaction temperature and time for preparing the oil-soluble PbSe/ZnS core-shell semiconductor quantum dots are shown in Table 4.
TABLE 4
Example 3 morphology characterization of PbSe/Metal sulfide core-shell semiconductor Quantum dots
The samples B1-B5 and M1-M5 are subjected to shape characterization by using a JEOL-JEM 2100F transmission electron microscope, typical representatives are shown in figure 1, and figure 1 is a transmission electron microscope image of PbSe/CdS core-shell quantum dots of the sample B2, so that the total diameter of the PbSe/CdS core-shell quantum dots is 6.5nm, the shell thicknesses are all 1-1.5nm, and the prepared quantum dot material is high in size uniformity.
The samples B6-B8 and M6-M8 are subjected to morphology characterization by using a JEOL-JEM 2100F transmission electron microscope, and are typically shown in FIG. 4, and FIG. 4 is a transmission electron microscope image of PbSe/ZnS core-shell quantum dots of the sample B8, so that the total diameter of the PbSe/ZnS core-shell quantum dots is 9.5nm, the shell thicknesses are both 2-4nm, and the prepared quantum dot material is high in size uniformity.
Example 4 absorption Spectroscopy testing of PbSe/Metal sulfide core-Shell semiconductor Quantum dots
The absorption spectrum tests of samples B1-B5 and M1-M5 are carried out by using an Shimadzu UV-3600 ultraviolet-visible near-infrared spectrophotometer, the samples B1-B5 are taken as typical representatives, and the absorption spectrum of PbSe/CdS core-shell quantum dots of the samples B1-B5 is shown in FIG. 2, and the absorption peaks of the quantum dots from left to right are 1470nm (corresponding to the sample B1), 1510nm (corresponding to the sample B2), 1590nm (corresponding to the sample B3), 1655nm (corresponding to the sample B4) and 1750nm (corresponding to the sample B5).
The samples B6-B8 and M6-M8 were subjected to absorption spectrum testing by using Shimadzu UV-3600 UV-visible near infrared spectrophotometer, and the samples B6-B8 are typically represented, and FIG. 5 shows the absorption spectrum of PbSe/ZnS core-shell quantum dots of the samples B6-B8, and it can be seen from the figure that the absorption peaks of the quantum dots from left to right are 1480nm (corresponding to sample B6), 1520nm (corresponding to sample B7) to 1560nm (corresponding to sample B8), respectively.
Example 5 fluorescence Spectroscopy 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, typically represented by samples B1-B5, and FIG. 3 shows a fluorescence spectrum of PbSe/CdS core-shell quantum dots of samples B1-B5, and as can be seen from the figure, the fluorescence peaks from left to right of the quantum dots 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, represented by sample B6-B8 as a representative, and FIG. 6 is a fluorescence spectrum diagram of PbSe/ZnS core-shell quantum dots of sample B6-B8, as can be seen from the diagram, the absorption peaks of the quantum dots from left to right are 1510nm (corresponding to sample B6) and 1560nm (corresponding to sample B7) to 1600nm (corresponding to sample B8).
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of PbSe/metal sulfide core-shell quantum dots is characterized by at least comprising the following steps:
(1) obtaining 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 of the alcohol-soluble PbSe quantum dot nano material contains a ligand, and the ligand comprises sulfydryl;
the metal precursor is at least one of cadmium metal precursor, zinc metal precursor and lead metal precursor.
2. The method 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 the metal precursor is 10mg:10-5～0.002mol；
Wherein the number of moles of the metal precursor is based on the number of moles 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 method according to claim 1, wherein the conditions of 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 organophosphinic agent; the organic phosphine reagent is selected from at least one of tri-n-octyl phosphine, tri-n-butyl phosphine, diphenyl phosphine, triethyl phosphine, trimethoxy phosphine and tri-p-phenyl methyl phosphine.
7. The method for preparing 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;
(IV) mixing the first solution and the second solution to obtain the mixture, and reacting the mixture I in an inert atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot;
preferably, the step (iv) includes: adding an organic phosphine reagent into the mixture, and reacting in an inactive atmosphere to obtain the PbSe/metal sulfide core-shell quantum dot;
preferably, in the first solution, the ratio of the mass of the alcohol-soluble PbSe quantum dot nanomaterial to the volume of the polar solvent is 10mg: 1-6 mL;
preferably, in the second solution, the ratio of the number of moles of the metal precursor to the volume of the polar solvent is 10-5～0.002mol：0.5～3mL；
Preferably, 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 alcohol compound and a polar solvent, and reacting III to obtain the alcohol-soluble PbSe quantum dot nano material;
preferably, the conditions of the reaction III are: the reaction temperature is 0-180 ℃; the reaction time is 5-50 min;
preferably, the PbSe/metal sulfide core-shell quantum dots obtained in the step (2) are alcohol-soluble PbSe/metal sulfide core-shell quantum dots;
preferably, the step (2) includes:
(2-1) reacting the mixture containing the alcohol-soluble PbSe quantum dot nano material, the metal precursor and the polar solvent to obtain alcohol-soluble PbSe/metal sulfide core-shell quantum dots;
(2-2) mixing the alcohol-soluble PbSe/metal sulfide nuclear shell quantum dots with an organic amine compound and a nonpolar solvent, and reacting II to obtain the PbSe/metal sulfide nuclear shell quantum dots; the PbSe/metal sulfide nuclear shell quantum dots are oil-soluble PbSe/metal sulfide nuclear shell quantum dots;
preferably, in the step (2-2), the ratio of the mass of the alcohol-soluble PbSe/metal sulfide core-shell quantum dots to the volume of the organic amine compound to 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 and chloroform;
preferably, the conditions of the reaction II are: the reaction temperature is 0-150 ℃; the reaction time is 5-50 min;
preferably, the organic amine compound is at least one selected from octylamine, oleylamine, dodecylamine, octadecylamine and trioctylamine.
8. A PbSe/metal sulfide core-shell quantum dot, which is characterized in that the PbSe/metal sulfide core-shell quantum dot is at least one selected from PbSe/metal sulfide core-shell quantum dots prepared by the preparation method according to any one of claims 1 to 7.
9. The PbSe/metal sulfide core-shell quantum dot of claim 8, wherein the PbSe/metal sulfide core-shell quantum dot is a core-shell structure of a metal sulfide-coated PbSe quantum dot nanomaterial;
wherein, the core is a PbSe quantum dot nano material, and the shell is a metal sulfide;
preferably, the thickness of the shell layer of the core-shell structure is 0.1-6.0 nm.
10. The PbSe/metal sulfide core-shell quantum dot prepared by the preparation method according to any one of claims 1 to 7 and the application of the PbSe/metal sulfide core-shell quantum dot according to claim 8 or 9 in the fields of photoelectric devices, nano devices and sensing.
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