CN116161695A - Method for synthesizing high-quality monodisperse PbS quantum dots - Google Patents

Method for synthesizing high-quality monodisperse PbS quantum dots Download PDF

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CN116161695A
CN116161695A CN202310100096.8A CN202310100096A CN116161695A CN 116161695 A CN116161695 A CN 116161695A CN 202310100096 A CN202310100096 A CN 202310100096A CN 116161695 A CN116161695 A CN 116161695A
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quantum dots
pbs quantum
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李京波
张梦龙
王创垒
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Zhejiang Xinke Semiconductor Co Ltd
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Zhejiang Xinke Semiconductor Co Ltd
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    • C01G21/00—Compounds of lead
    • C01G21/21—Sulfides
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/661—Chalcogenides
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The application discloses a method for synthesizing high-quality monodisperse PbS quantum dots, which comprises the following steps: s1, dissolving phenyl isocyanate in a toluene solvent to form a solution A; s2, dissolving amines in toluene to form a solution B; s3, mixing, stirring and drying the solution A and the solution B to obtain a disubstituted thiourea reactant; s4, mixing lead halide with oleylamine, removing water and oxygen, and heating the precursor solution to 100-180 ℃ in an inert gas atmosphere to form a solution C; s5, dissolving the disubstituted thiourea in an alkane solvent, then injecting the alkane solvent into the solution C, and quenching the solution in an ice water bath after the reaction is carried out for a set time to obtain a mixed solution; s6, removing impurities after the reaction is finished. The application improves the precursor of the sulfur source, selects the low-cost and air-stable disubstituted thiourea library as the precursor of the sulfur source, and can control the activity of the synthesis reaction by adjusting the organic substituent of the disubstituted thiourea. Second, the lead precursor is a lead halide, which can enhance the stability of the quantum dot in air.

Description

Method for synthesizing high-quality monodisperse PbS quantum dots
Technical Field
The invention relates to the field of preparation of compound semiconductor materials, in particular to a method for synthesizing high-quality monodisperse PbS quantum dots.
Background
Lead sulfide (PbS) nanocrystals, also known as Quantum Dots (QDs), have a size-dependent, tunable near-infrared bandgap, which makes them of great application potential in photovoltaic, photodetector, and infrared light emission. In most of these applications, the quantum dots with monodispersity, that is, almost all the quantum dots have the same size, can well improve the performance of the quantum dot device. For example, for photovoltaic devices, the monodispersity creates a uniform energy distribution that maximizes the rate at which charge carriers are extracted from the quantum dot film. For infrared light detection and emission, monodispersity provides narrow and well controlled absorption and emission. In corresponding visible cadmium sulfide/cadmium selenide (CdS/CdSe) quantum dots, narrow emission line width has become a fundamental feature of commercial viability.
Despite the numerous advantages of monodisperse quantum dots, current methods of synthesizing lead sulfide quantum dots have fallen behind cadmium selenide and lead selenide (PbSe) in terms of the monodispersity achievable over a wide band gap. While the bandgaps of PbS and PbSe quantum dots can be tuned within similar ranges, pbS has unique advantages over PbSe in optoelectronic devices, such as improved air stability, and higher abundance/lower cost of sulfur compared to selenium.
Currently, the most widely used sulfide precursors include bis (trimethylsilyl) sulfide [ (TMS) 2 S]Phosphine sulfide (R) 3 P=s, where R represents an alkyl group or an aryl group), and hydrogen sulfide produced by heating elemental sulfur in an alkane or amine solvent. Depending on the crystallization conditions, a precursor is selected that provides the necessary monomer supply rate. For example, (TMS) 2 S generally reacts rapidly with metal salts, making it available for use near room temperature; however, rapid reactivity can lead to mixing limitations during the injection step, impeding the scale of the reaction. Phosphine sulfide derivatives, on the other hand, typically react slowly up to about 300 ℃ and the reaction yield is low. Although the reaction of elemental sulfur with alkanes and amines is more versatile and can be used at intermediate temperatures, they areThe conversion reaction follows an undefined radical route, is difficult to control and is sensitive to the presence of impurities. In addition, sulfur-containing byproducts can cause batch-to-batch variation and adversely affect the properties of the nanocrystals.
Disclosure of Invention
The invention aims at the problems and overcomes at least one defect, and provides a method for synthesizing high-quality monodisperse PbS quantum dots.
The technical scheme adopted by the invention is as follows:
a method for synthesizing high-quality monodisperse PbS quantum dots comprises the following steps:
s1, dissolving a mmol of phenyl isocyanate sulfate in b mL of toluene solvent to form a solution A, wherein the ratio of a to b is (30-80): (10-40);
s2, dissolving c mmol of amine in d mL of toluene to form solution B, wherein the ratio of c to d is (30-80): (10-40);
s3, mixing and stirring the solution A and the solution B; drying after the reaction is finished to obtain a disubstituted thiourea reactant;
s4, mixing e mmol of lead halide with f mL of oleylamine, wherein the ratio of e to f is (30-60): (20-50), removing water and oxygen to obtain a precursor solution, and heating the precursor solution to 100-180 ℃ in an inert gas atmosphere to form a solution C;
s5, according to the precursor proportion of lead and sulfur (12-30): 1, dissolving disubstituted thiourea in an alkane solvent, then injecting the alkane solvent into a solution C, and quenching the solution in an ice water bath after the reaction is carried out for a set time to obtain a mixed solution;
s6, after the reaction is finished, injecting normal hexane and oleic acid into the mixed solution, centrifuging to remove unreacted impurities, adding an anti-solvent into the supernatant after centrifuging, centrifuging again to collect the precipitate, and dispersing the precipitate in a weak polar solvent.
The application improves the precursor of the sulfur source, selects the low-cost and air-stable disubstituted thiourea library as the precursor of the sulfur source, and can control the activity of the synthesis reaction by adjusting the organic substituent of the disubstituted thiourea. Second, the monodispersity of the reaction product is better controlled by controlling the molar ratio of the precursors (Pb: S). In addition, since the lead precursor is lead halide, the synthesized quantum dot surface can be passivated by halogen anions, which can enhance the stability of the quantum dot in air.
The PbS quantum dot synthesized by the method has obvious Tyndall effect, and no sedimentation occurs after being stored in the air for several months. The synthetic method has the advantages of simple flow, easy control, strong repeatability and low material cost, and is suitable for large-scale production.
Drawings
In an embodiment of the invention, in the step S3, the stirring time is 2-6h.
In one embodiment of the present invention, in the step S3, the drying manner is as follows: vacuum drying at normal temperature for 12-24 h.
In an embodiment of the invention, the amine in the step S2 is hexylamine, octylamine, dodecylamine, octadecylamine or octadecylamine.
In one embodiment of the present invention, the amine in the step S2 is N-tetradecylamine, and the di-substituted thiourea reactant is an N-tetradecyl-N' -phenylthiourea product.
In an embodiment of the present invention, in the step S4, the lead halide is lead chloride; the lead halide and oleylamine were mixed in a three-necked flask.
In one embodiment of the present invention, in the step S5, the set time is 20-40min.
In one embodiment of the present invention, in the step S5, 2-4mmol of the disubstituted thiourea is dissolved in an alkane solvent.
In one embodiment of the present invention, in the step S6, 50-100mL of n-hexane is injected into the mixed solution, and 5-10mL of oleic acid is injected.
In an embodiment of the invention, in the step S6, the antisolvent is ethanol or isopropanol; the weak polar solvent is hexane, octane or toluene.
The beneficial effects of the invention are as follows: the application improves the precursor of the sulfur source, selects the low-cost and air-stable disubstituted thiourea library as the precursor of the sulfur source, and can control the activity of the synthesis reaction by adjusting the organic substituent of the disubstituted thiourea. Second, the monodispersity of the reaction product is better controlled by controlling the molar ratio of the precursors (Pb: S). In addition, since the lead precursor is lead halide, the synthesized quantum dot surface can be passivated by halogen anions, which can enhance the stability of the quantum dot in air.
Fig. 1 is a physical diagram of PbS quantum dot sol prepared by the present application;
fig. 2 is a TEM image of PbS quantum dots made by the present application;
FIG. 3 is an HR-TEM image of PbS quantum dots made according to the present application;
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the embodiments described are some, but not all, of the embodiments of the present application. The components of the embodiments of the present application, which are generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations.
In the description of the present application, it should be noted that, the azimuth or positional relationship indicated by the terms "inner", "outer", etc. are based on the azimuth or positional relationship shown in the drawings, or the azimuth or positional relationship that is commonly put when the product of the application is used, are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and therefore should not be construed as limiting the present application. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In the description of the present application, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art in a specific context.
The present invention will be described in detail with reference to the accompanying drawings.
A method for synthesizing high-quality monodisperse PbS quantum dots comprises the following steps:
synthesis of air-stable disubstituted thioureas:
s1, dissolving a mmol of phenyl isocyanate sulfate in b mL of toluene solvent to form a solution A, wherein the ratio of a to b is (30-80): (10-40);
s2, dissolving c mmol of amine in d mL of toluene to form solution B, wherein the ratio of c to d is (30-80): (10-40);
s3, mixing and stirring the solution A and the solution B; drying after the reaction is finished to obtain a disubstituted thiourea reactant;
preparing a lead halide liquid:
s4, mixing e mmol of lead halide with f mL of oleylamine, wherein the ratio of e to f is (30-60): (20-50), removing water and oxygen to obtain a precursor solution, and heating the precursor solution to 100-180 ℃ in an inert gas atmosphere to form a solution C;
s5, according to the precursor proportion of lead and sulfur (12-30): 1, dissolving disubstituted thiourea in an alkane solvent, then injecting the alkane solvent into a solution C, and quenching the solution in an ice water bath after the reaction is carried out for a set time to obtain a mixed solution;
s6, after the reaction is finished, injecting normal hexane and oleic acid into the mixed solution, centrifuging to remove unreacted impurities, adding an anti-solvent into the supernatant after centrifuging, centrifuging again to collect the precipitate, and dispersing the precipitate in a weak polar solvent.
The application improves the precursor of the sulfur source, selects the low-cost and air-stable disubstituted thiourea library as the precursor of the sulfur source, and can control the activity of the synthesis reaction by adjusting the organic substituent of the disubstituted thiourea. Second, the monodispersity of the reaction product is better controlled by controlling the molar ratio of the precursors (Pb: S). In addition, since the lead precursor is lead halide, the synthesized quantum dot surface can be passivated by halogen anions, which can enhance the stability of the quantum dot in air.
The PbS quantum dot synthesized by the method has obvious Tyndall effect, and no sedimentation occurs after being stored in the air for several months. The synthetic method has the advantages of simple flow, easy control, strong repeatability and low material cost, and is suitable for large-scale production.
Drawings
In this example, in step S3, the stirring time is 2-6 hours.
In this embodiment, in step S3, the drying method is as follows: vacuum drying at normal temperature for 12-24 h.
In practical use, the amine in step S2 may be hexylamine, octylamine, dodecylamine, octadecylamine, or octadecylenamine. In this example, the amine in step S2 is N-tetradecylamine and the di-substituted thiourea reactant is N-tetradecyl-N' -phenylthiourea product.
In this embodiment, in step S4, the lead halide is lead chloride; the lead halide and oleylamine were mixed in a three-necked flask.
In this embodiment, in step S5, the set time is 20-40min.
In this example, in step S5, 2-4mmol of the disubstituted thiourea is dissolved in an alkane solvent.
In this example, in step S6, 50-100mL of n-hexane was injected into the mixed solution, and 5-10mL of oleic acid was injected.
In the embodiment, in step S6, the antisolvent is ethanol or isopropanol; the weak polar solvent is hexane, octane or toluene.
The foregoing is only the preferred embodiments of the present invention, and therefore, the scope of the present invention is not limited by the above description, but is also included in the scope of the present invention as long as the equivalent structural changes made in the present invention description and the accompanying drawings are directly or indirectly applied to other related technical fields.

Claims (10)

1. The method for synthesizing the high-quality monodisperse PbS quantum dots is characterized by comprising the following steps of:
s1, dissolving a mmol of phenyl isocyanate sulfate in b mL of toluene solvent to form a solution A, wherein the ratio of a to b is (30-80): (10-40);
s2, dissolving c mmol of amine in d mL of toluene to form solution B, wherein the ratio of c to d is (30-80): (10-40);
s3, mixing and stirring the solution A and the solution B; drying after the reaction is finished to obtain a disubstituted thiourea reactant;
s4, mixing e mmol of lead halide with f mL of oleylamine, wherein the ratio of e to f is (30-60): (20-50), removing water and oxygen to obtain a precursor solution, and heating the precursor solution to 100-180 ℃ in an inert gas atmosphere to form a solution C;
s5, according to the precursor proportion of lead and sulfur (12-30): 1, dissolving disubstituted thiourea in an alkane solvent, then injecting the alkane solvent into a solution C, and quenching the solution in an ice water bath after the reaction is carried out for a set time to obtain a mixed solution;
s6, after the reaction is finished, injecting normal hexane and oleic acid into the mixed solution, centrifuging to remove unreacted impurities, adding an anti-solvent into the supernatant after centrifuging, centrifuging again to collect the precipitate, and dispersing the precipitate in a weak polar solvent.
2. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein in the step S3, the stirring time is 2-6h.
3. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein in step S3, the drying manner is as follows: vacuum drying at normal temperature for 12-24 h.
4. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein the amine in step S2 is hexylamine, octylamine, dodecylamine, octadecylamine or octadecylenamine.
5. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 4, wherein the amine in step S2 is N-tetradecylamine and the di-substituted thiourea reactant is N-tetradecyl-N' -phenylthiourea product.
6. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein in step S4, the lead halide is lead chloride; the lead halide and oleylamine were mixed in a three-necked flask.
7. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein the set time in step S5 is 20-40min.
8. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein 2-4mmol of the disubstituted thiourea is dissolved in an alkane solvent in step S5.
9. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein in step S6, 50-100mL of n-hexane and 5-10mL of oleic acid are injected into the mixed solution.
10. The method for synthesizing high-quality monodisperse PbS quantum dots according to claim 1, wherein in step S6, the antisolvent is ethanol or isopropanol; the weak polar solvent is hexane, octane or toluene.
CN202310100096.8A 2023-02-02 2023-02-02 Method for synthesizing high-quality monodisperse PbS quantum dots Pending CN116161695A (en)

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