CN110835109B - Novel two-dimensional layered semiconductor material and preparation method thereof - Google Patents
Novel two-dimensional layered semiconductor material and preparation method thereof Download PDFInfo
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- CN110835109B CN110835109B CN201810937272.2A CN201810937272A CN110835109B CN 110835109 B CN110835109 B CN 110835109B CN 201810937272 A CN201810937272 A CN 201810937272A CN 110835109 B CN110835109 B CN 110835109B
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Abstract
The invention discloses a novel two-dimensional layered semiconductor material and a preparation method thereof. The two-dimensional semiconductor material can be stripped through a solvent liquid phase to obtain a few-layer or multi-layer two-dimensional nanosheet, and has great potential in nanoelectronic application.
Description
Technical Field
The invention belongs to the technical field of two-dimensional layered semiconductor materials and preparation thereof, and relates to a novel IV-V group binary two-dimensional layered semiconductor material XBI (X ═ Si, Ge, Sn), in particular to a novel two-dimensional layered semiconductor material XBI (X ═ Si, Ge, Sn) and a preparation method thereof.
Background
In recent years, with the rapid development of the field of two-dimensional materials, people find more and more two-dimensional layered semiconductor materials through continuous theoretical calculation and experimental exploration. The unique structural features of these two-dimensional materials give them a rich physical connotation and excellent physicochemical properties. Has wide application prospect in the fields of next generation photoelectric information functional materials, energy storage, biological sensing devices and the like. In 2018, Yan et al proposed a novel two-dimensional single-layer IV-V group binary semiconductor material XBI (X ═ Si, Ge and Sn) through theoretical calculation, and proved through calculation that the single-layer semiconductor material in which the single-layer SiBi is a direct bandgap semiconductor with a bandgap of 0.226eV, and in which the single-layer GeBi and SnBi are indirect bandgap semiconductors with bandgaps of 0.062 and 0.132eV respectively, has great potential in nanoelectronic applications. However, the novel two-dimensional material has no experimental result support.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a novel two-dimensional layered semiconductor material XBI (X ═ Si, Ge, Sn) and a preparation method thereof, and proves that the novel two-dimensional IV-V group binary semiconductor material XBI (X ═ Si, Ge, Sn) exists, a layered structure material can be obtained through high-temperature sintering, and a few-layer or multi-layer structure can be obtained through stripping.
The technical purpose of the invention is realized by the following technical scheme:
the two-dimensional layered semiconductor material and the preparation method thereof are carried out according to the following steps: uniformly mixing a metal simple substance Bi and a simple substance X according to an equal molar ratio, placing the mixture into a vacuum sealed quartz tube, placing the quartz tube into a heating device for high-temperature sintering reaction, and obtaining a two-dimensional layered semiconductor material after the reaction is finished, wherein the simple substance X is Si, Ge or Sn, and the high-temperature sintering parameters are as follows: raising the temperature from room temperature (20-25 ℃) to 1000 ℃ and 1200 ℃ at the speed of 0.5-5 ℃/min, preserving the temperature for 20-80 h, and then lowering the temperature to room temperature (20-25 ℃) at the speed of 0.5-5 ℃/min.
Moreover, the high-temperature sintering parameters: heating from room temperature (20-25 deg.C) to 1000-.
Moreover, the high-temperature sintering parameters: heating from room temperature (20-25 deg.C) to 1000-1100 deg.C at a speed of 1-3 deg.C/min, maintaining for 30-60h, and cooling to room temperature (20-25 deg.C) at a speed of 1-3 deg.C/min.
And breaking the quartz tube after the reaction is finished to obtain a product with metallic luster, namely the two-dimensional IV-V group binary semiconductor material is prepared. The product can be stripped through a solvent liquid phase to obtain few-layer or multi-layer two-dimensional nanosheets, and the microstructure of the two-dimensional layered semiconductor material is proved to be a layered structure, as shown in figure 4.
XRD characterization is carried out on the product prepared by the method disclosed by the invention, as shown in figure 1, the product is mainly oriented along a plurality of crystal planes and has good crystallinity, and the crystallization peak of the product is completely different from that of the original reactant simple substance, so that the reactant generates a new structure, namely a target product through reaction. The three products SiBi, GeBi and SnBi have similar crystallization peak shapes, which shows that the three products SiBi, GeBi and SnBi have similar crystal structures. As can be seen from the scanning electron microscope image in FIG. 2, the three products SiBi, GeBi and SnBi all have obvious layered structures. After NMP solvent liquid phase stripping, the obtained sample dispersion liquid is coated on a silicon chip in a spinning mode and observed through an optical microscope, the fact that the sample is a thin-layer nanosheet can be obviously seen, and the fact that the thin-layer nanosheet can be easily obtained through liquid phase stripping of a layered sample obtained through high-temperature sintering reaction is demonstrated.
The invention provides a novel two-dimensional layered semiconductor material XBI (X ═ Si, Ge and Sn) and a preparation method thereof, which proves that the novel two-dimensional IV-V group binary semiconductor material XBI (X ═ Si, Ge and Sn) exists, a layered structure material can be obtained through high-temperature sintering, and a few-layer or multi-layer structure can be obtained through stripping.
Drawings
FIG. 1 is an XRD spectrum of SiBi, GeBi and SnBi products prepared by the invention.
FIG. 2 is a scanning electron microscope image of SiBi, GeBi and SnBi products prepared by the invention.
FIG. 3 is a photograph taken by an optical microscope, wherein nanosheets obtained by solvent liquid phase stripping of SiBi, GeBi and SnBi prepared by the invention are spin-coated on a silicon wafer.
FIG. 4 is a transmission electron microscope image of few-layer nanosheets obtained after GeBi stripping of the product prepared in the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments. The following examples of the present invention are given to further illustrate the invention, but not to limit the scope of the invention.
Example 1
118.6mg (0.0042mol) of Si and 881.9mg of Bi (0.0042mol) are weighed and sealed in a quartz tube in vacuum, then the quartz tube is put into a tube furnace or a box furnace, the temperature is raised from room temperature to 1200 ℃ at the speed of 0.5 ℃/min and is kept for 24h, and then the temperature is lowered to the room temperature at the speed of 0.5 ℃/min. After the reaction is finished, the quartz tube is broken, and a product (SiBi) with metallic luster is obtained.
Example 2
257.9mg (0.00355mol) of Ge and 742.1mg (0.00355mol) of Bi are weighed, sealed in a quartz tube in vacuum, then put into a tube furnace or a box furnace, heated from room temperature to 1100 ℃ at the speed of 1 ℃/min, kept for 48h, and then cooled to room temperature at the speed of 1 ℃/min. After the reaction is finished, the quartz tube is broken, and a product (GeBi) with metallic luster is obtained.
Example 3
362.2mg (0.00305mol) of Sn and 637.7mg (0.00305mol) of Bi are weighed, sealed in a quartz tube in vacuum, then put into a tube furnace or a box furnace, heated from room temperature to 1000 ℃ at the speed of 1.5 ℃/min, kept for 72h, and then cooled to room temperature at the speed of 1.5 ℃/min. After the reaction is finished, the quartz tube is broken, and a product (SnBi) with metallic luster is obtained.
And (3) stripping the solvent liquid phase of the obtained SiBi, GeBi and SnBi products: 20mg of sample are weighed, dispersed in 15ml of NMP (N-methylpyrrolidone) solvent, sonicated on a sonication cell disruptor at 20% power for 2h and then at 3000rmin -1 Centrifuging for 15min on a centrifuge at a rotating speed to obtain supernatant, namely the dispersion of the nanosheets stripped in liquid phase. The dispersion can be spin-coated on a silicon wafer, and then the stripping effect is observed through an optical microscope, so that few-layer or multi-layer two-dimensional nanosheets are displayed.
According to the invention, the preparation of the two-dimensional layered semiconductor material can be realized by adjusting the preparation process parameters, and the liquid phase shows few layers or multi-layer two-dimensional nano-sheets after being stripped, thereby showing the performance basically similar to that of the embodiment. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (6)
1. The two-dimensional layered semiconductor material is characterized in that the two-dimensional layered semiconductor material is a two-dimensional IV-V group binary semiconductor material, a multilayer two-dimensional nanosheet is obtained through solvent liquid phase stripping, and the method comprises the following steps: uniformly mixing a metal simple substance Bi and a simple substance X according to an equal molar ratio, placing the mixture into a vacuum sealed quartz tube, placing the quartz tube into a heating device for high-temperature sintering reaction, and obtaining a two-dimensional layered semiconductor material after the reaction is finished, wherein the simple substance X is Si, Ge or Sn, and the high-temperature sintering parameters are as follows: raising the temperature from 20-25 ℃ to 1000-1200 ℃ at the speed of 0.5-5 ℃/min, preserving the temperature for 20-80 h, and then lowering the temperature to 20-25 ℃ at the speed of 0.5-5 ℃/min.
2. The two-dimensional layered semiconductor material according to claim 1, wherein the high temperature sintering parameters are: heating from 20-25 deg.C to 1000-1200 deg.C at a rate of 0.5-1.5 deg.C/min, maintaining for 24-72h, and cooling to 20-25 deg.C at a rate of 0.5-1.5 deg.C/min.
3. The two-dimensional layered semiconductor material of claim 1, wherein the high temperature sintering parameters are: heating from 20-25 ℃ to 1000-1100 ℃ at the speed of 1-3 ℃/min, preserving the heat for 30-60h, and then cooling to 20-25 ℃ at the speed of 1-3 ℃/min.
4. The preparation method of the two-dimensional layered semiconductor material is characterized by comprising the following steps of: uniformly mixing a metal simple substance Bi and a simple substance X according to an equal molar ratio, placing the mixture into a vacuum sealed quartz tube, placing the quartz tube into a heating device for high-temperature sintering reaction, and obtaining a two-dimensional layered semiconductor material after the reaction is finished, wherein the simple substance X is Si, Ge or Sn, and the high-temperature sintering parameters are as follows: raising the temperature from 20-25 ℃ to 1000-1200 ℃ at the speed of 0.5-5 ℃/min, preserving the temperature for 20-80 h, and then lowering the temperature to 20-25 ℃ at the speed of 0.5-5 ℃/min.
5. The method for preparing a two-dimensional layered semiconductor material according to claim 4, wherein the parameters of the high-temperature sintering are as follows: heating from 20-25 deg.C to 1000-1200 deg.C at a rate of 0.5-1.5 deg.C/min, maintaining for 24-72h, and cooling to 20-25 deg.C at a rate of 0.5-1.5 deg.C/min.
6. The method for preparing a two-dimensional layered semiconductor material according to claim 4, wherein the parameters of the high-temperature sintering are as follows: heating from 20-25 ℃ to 1000-1100 ℃ at the speed of 1-3 ℃/min, preserving the heat for 30-60h, and then cooling to 20-25 ℃ at the speed of 1-3 ℃/min.
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