CN112299383A - Method for preparing two-dimensional layered material by stripping ternary atomic crystal - Google Patents
Method for preparing two-dimensional layered material by stripping ternary atomic crystal Download PDFInfo
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- CN112299383A CN112299383A CN201910707739.9A CN201910707739A CN112299383A CN 112299383 A CN112299383 A CN 112299383A CN 201910707739 A CN201910707739 A CN 201910707739A CN 112299383 A CN112299383 A CN 112299383A
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- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a method for preparing a two-dimensional layered material by stripping a ternary atomic crystal, which comprises the steps of taking a GeSeTe crystal as a precursor, dispersing the GeSeTe crystal in a small bottle filled with an isopropanol solvent, degassing by using argon, sealing by using a Teflon adhesive tape, carrying out ultrasonic treatment for 6h, avoiding overheating of a bathtub and liquid, keeping the temperature at 10 ℃ by water cooling, and then carrying out centrifugal separation to obtain the two-dimensional layered semiconductor material 2D-GeSeTe. Similar to transition metal chalcogenide GeSn, GeS and the like, the ternary crystal has a proper optical band gap and can be used in the fields of photoelectric devices, photocatalysis and the like.
Description
Technical Field
The invention belongs to the preparation of novel two-dimensional materials, and particularly relates to a simple preparation method for obtaining a two-dimensional material by stripping a novel ternary crystal from top to bottom by a solution method.
Background
Two-dimensional layered semiconductor material, in particular chalcogenThe compound (2DLMCs) are stripped to two-dimensional layers from a bulk phase, the thickness of the compound is continuously reduced, the optical band gap is gradually increased, and the direct band gap and the indirect band gap have an undetermined conversion relation. In addition, the ultra-thin structure based on the two-dimensional material brings different electronic structure and optical performance from bulk phase materials, has proper peeling energy, and has special phenomena such as quantum effect, energy valley effect and the like, thereby receiving wide attention of people. After the graphene is discovered, the two-dimensional material is rapidly explored and researched, wherein the two-dimensional layered transition metal sulfur compound (TMDCs: MoS) with the similar graphene structure and the adjustable band gap2、WS2Etc.), iii-iv group compounds (GeS, GeSe, etc.) and their related heterojunctions have become one of the research focuses in recent years, and have a great number of applications in the fields of photoelectronic devices, photocatalytic hydrogen production, etc. based on the difference of band gap size and valence band position.
In addition, compared with binary metal crystals, the preparation of ternary crystals is relatively more difficult, and comprises the problems of difficulty in uniform eutectic melting, difficulty in determining eutectic point and the like, and meanwhile, the Ge-based two-dimensional material is similar to black phosphene, is unstable in air, is easy to oxidize, and has fewer related reports. In 2008, UlrichHausssermann et al prepared a ternary metal precursor by arc remelting and stabilized it by hydrogenation on the basis of the work of the predecessors, to obtain a quaternary crystal AeGaEH (Ae: Ca, Sr, Ba; E: Si, Ge, Sn), in which BaGaSiH, the bulk material, had a band gap of 0.6 eV.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a two-dimensional layered material by stripping a ternary atomic crystal. Different from the prior preparation of two-dimensional materials, ternary crystals are selected in the preparation process, and the obtained novel two-dimensional material has good electrical property and optical property.
The technical purpose of the invention is realized by the following technical scheme.
A method for preparing a two-dimensional layered material by stripping a ternary atomic crystal is carried out according to the following steps: vacuum packaging and processing three metals Ge, Se and Te according to an equal molar ratio to obtain GeSeTe crystals, raising the temperature from 20-25 ℃ to 900-1000 ℃ within 350-450 min, maintaining the temperature for 1000-1200 min, and then cooling to 20-25 ℃ at the temperature of 0.5-1 ℃/min; the GeSeTe crystal is dispersed in isopropanol, degassed by inert protective atmosphere, sealed and continuously subjected to ultrasonic treatment, and meanwhile, water cooling is adopted to maintain the temperature at 10-15 ℃ so as to avoid overheating (such as bathtub and liquid overheating) in the ultrasonic treatment process, and finally, centrifugal separation is carried out to obtain the two-dimensional layered semiconductor material 2D-GeSeTe.
In the technical scheme, when three metals of Ge, Se and Te are subjected to vacuum packaging and processing, the vacuum degree is below 0.1 MPa.
In the technical scheme, the temperature is increased to 950-1000 ℃ within 380-400 min from 20-25 ℃, is maintained for 1100-1200 min, and is reduced to 20-25 ℃ at the speed of 0.5-1 ℃/min; a vacuum tube furnace is used as the processing equipment.
In the technical scheme, the inert protective atmosphere is nitrogen, helium or argon.
In the above technical scheme, degassing is performed by using an inert protective atmosphere, and then sealing is performed by using a Teflon tape.
In the technical scheme, the centrifugal rate is 3000-5000 rmp during centrifugal separation.
In the above technical scheme, the ultrasonic treatment time is 5 to 20 hours, preferably 10 to 15 hours.
In the above technical scheme, GeSeTe crystals are dispersed in isopropanol, and the ratio of the mass (mg) of the GeSeTe crystals to the volume (ml) of the isopropanol is (1-3): 1, preferably (1-2): 1.
compared with a binary precursor material for preparing a two-dimensional material, in the technical scheme of the invention, GeSeTe is used as a precursor, the GeSeTe is directly dispersed in an isopropanol solvent, and centrifugal treatment (stripping) is carried out after ultrasonic treatment to obtain the ternary crystal two-dimensional material (namely, the ternary precursor is prepared firstly, and the two-dimensional material is prepared by a solution method). Ternary crystals are selected in the preparation process, and the obtained novel two-dimensional material has good electrical property and optical property.
Description of the drawings:
FIG. 1 shows a scanning electron micrograph and mapping of GeSeTe bulk phase material obtained by the present invention.
FIG. 2 is an XRD spectrum diagram of GeSeTe crystal obtained by the present invention.
FIG. 3 is an optical microscopic image of the GeSeTe layered material obtained in the present invention before and after exfoliation.
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 present invention, but not to limit the scope of the present invention.
Example 1
Weighing 10mmol Ge, 10mmol Se and 10mmol Te in a glove box in turn, adding into a quartz tube in turn, sealing by using a vacuum melting packaging device, sintering in a vacuum tube furnace, heating from normal temperature to 950 ℃ in 400min, maintaining for 1200min, and cooling to normal temperature at 0.5 ℃/min. Dispersing 30mg of the precursor in a 50ml transparent glass bottle filled with 30ml of isopropanol, sealing with Teflon adhesive tape after degassing with argon, ultrasonically treating for 6h to avoid overheating of a bathtub and liquid, and centrifuging for 20min in a desktop centrifuge of 3000rmp at room temperature under water cooling at 10 ℃ to obtain the 2D-GeSeTe layered material.
Example 2
Weighing 10mmol Ge, 10mmol Se and 10mmol Te in a glove box in turn, adding into a quartz tube in turn, sealing by using a vacuum melting packaging device, sintering in a vacuum tube furnace, heating to 1000 ℃ from normal temperature for 450min, maintaining for 1000min, and cooling to normal temperature at 0.5 ℃/min. Dispersing 30mg of the precursor in a 50ml transparent glass bottle filled with 30ml of isopropanol, sealing with a Teflon adhesive tape after degassing with argon, carrying out ultrasonic treatment for 10h to avoid overheating of a bathtub and liquid, and centrifuging for 30min in a desktop centrifuge of 3000rmp at room temperature under water cooling at 10 ℃ to obtain the 2D-GeSeTe layered material.
Example 3
Weighing 10mmol Ge, 10mmol Se and 10mmol Te in a glove box in turn, adding into a quartz tube in turn, sealing by using a vacuum melting packaging device, sintering in a vacuum tube furnace, raising the temperature from normal temperature to 900 ℃ for 350min, maintaining the temperature for 1200min, and then cooling to normal temperature at the rate of 0.5 ℃/min. Dispersing 30mg of the precursor in a 50ml transparent glass bottle filled with 30ml of isopropanol, sealing with a Teflon adhesive tape after degassing with argon, ultrasonically treating for 5h to avoid overheating of a bathtub and liquid, and centrifuging for 20min in a desktop centrifuge of 5000rmp at room temperature under water cooling at 10 ℃ to obtain the 2D-GeSeTe layered material.
Example 4
Weighing 10mmol Ge, 10mmol Se and 10mmol Te in a glove box in turn, adding into a quartz tube in turn, sealing by using a vacuum melting and packaging device, sintering in a vacuum tube furnace, heating from room temperature to 960 deg.C for 420min, maintaining for 1200min, and cooling to room temperature at 0.5 deg.C/min. And (3) dispersing 30mg of the precursor into a 50ml transparent glass bottle filled with 30ml of isopropanol, sealing the bottle with a Teflon adhesive tape after argon degassing, ultrasonically treating the bottle for 15h to avoid overheating of a bathtub and liquid, and centrifuging the bottle for 30min in a 4000rmp bench centrifuge at room temperature by water cooling at 10 ℃ to obtain the 2D-GeSeTe layered material.
Example 5
Weighing 10mmol Ge, 10mmol Se and 10mmol Te in a glove box in turn, adding into a quartz tube in turn, sealing by using a vacuum melting packaging device, sintering in a vacuum tube furnace, heating to 980 ℃ from normal temperature for 450min, maintaining for 1150min, and cooling to normal temperature at 0.5 ℃/min. And (3) dispersing 30mg of the precursor into a 50ml transparent glass bottle filled with 30ml of isopropanol, sealing the bottle with a Teflon adhesive tape after argon degassing, ultrasonically treating the bottle for 8 hours to prevent the bathtub and the liquid from being overheated, and centrifuging the bottle for 20 minutes in a 4000rmp bench centrifuge at room temperature by water cooling at 10 ℃ to obtain the 2D-GeSeTe layered material.
Example 6
Weighing 10mmol Ge, 10mmol Se and 10mmol Te in a glove box in turn, adding into a quartz tube in turn, sealing by using a vacuum melting packaging device, sintering in a vacuum tube furnace, heating from normal temperature to 950 ℃ in 400min, maintaining for 1050min, and cooling to normal temperature at 0.5 ℃/min. And (3) dispersing 30mg of the precursor into a 50ml transparent glass bottle filled with 25ml of isopropanol, sealing the bottle with a Teflon adhesive tape after argon degassing, ultrasonically treating the bottle for 6h to avoid overheating of a bathtub and liquid, and centrifuging the bottle for 30min in a desktop centrifuge of 5000rmp at room temperature by water cooling at 10 ℃ to obtain the 2D-GeSeTe layered material.
The preparation of the 2D-GeSeTe layered material can be realized by adjusting the process parameters according to the content of the invention, the performance is consistent with that of the invention through testing, the three elements Ge, Se and Te are uniformly distributed on the material to present a GeSeTe crystal form, and the 2D-GeSeTe presents the appearance of the layered material after the solution stripping.
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 (7)
1. A method for preparing a two-dimensional layered material by peeling a ternary atomic crystal is characterized by comprising the following steps of: vacuum packaging and processing three metals Ge, Se and Te according to an equal molar ratio to obtain GeSeTe crystals, raising the temperature from 20-25 ℃ to 900-1000 ℃ within 350-450 min, maintaining the temperature for 1000-1200 min, and then cooling to 20-25 ℃ at the temperature of 0.5-1 ℃/min; the GeSeTe crystal is dispersed in isopropanol, degassed by inert protective atmosphere, sealed and continuously subjected to ultrasonic treatment, and meanwhile, water cooling is adopted to maintain the temperature at 10-15 ℃ so as to avoid overheating (such as bathtub and liquid overheating) in the ultrasonic treatment process, and finally, centrifugal separation is carried out to obtain the two-dimensional layered semiconductor material 2D-GeSeTe.
2. The method for preparing a two-dimensional layered material by stripping of the ternary atomic crystal as claimed in claim 1, wherein the vacuum degree is below 0.1MPa when the three metals Ge, Se and Te are subjected to vacuum packaging and processing.
3. The method for preparing two-dimensional layered material by stripping ternary atomic crystal as claimed in claim 1, wherein the temperature is raised to 950-1000 ℃ from 20-25 ℃ within 380-400 min, maintained for 1100-1200 min, and then lowered to 20-25 ℃ at 0.5-1 ℃/min.
4. The method for preparing two-dimensional layered material by peeling ternary atomic crystal according to claim 1, wherein the inert protective atmosphere is nitrogen, helium or argon.
5. The method for preparing a two-dimensional layered material by peeling the ternary atomic crystal as claimed in claim 1, wherein the centrifugation rate is 3000-5000 rmp.
6. The method for preparing a two-dimensional layered material by peeling of a ternary atomic crystal according to claim 1, wherein the ultrasonic treatment time is 5 to 20 hours, preferably 10 to 15 hours.
7. The method for preparing a two-dimensional layered material by ternary atomic crystal exfoliation according to claim 1, characterized in that GeSeTe crystals are dispersed in isopropanol, and the ratio of the mass (mg) of the GeSeTe crystals to the volume (ml) of the isopropanol is (1-3): 1, preferably (1-2): 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103692763A (en) * | 2013-12-06 | 2014-04-02 | 深圳先进技术研究院 | Peeling method of two-dimensional layered nano material |
| CN104973593A (en) * | 2015-06-18 | 2015-10-14 | 湖南大学 | Stripping method of stratified materials |
| CN105506742A (en) * | 2015-12-11 | 2016-04-20 | 山东大学 | Orthorhombic-phase two-dimension-layered SiP2 single-crystal thin film, and preparation method and application thereof |
| CN108611684A (en) * | 2018-04-27 | 2018-10-02 | 清华-伯克利深圳学院筹备办公室 | A kind of controllable thining method of Transition-metal dichalcogenide two-dimensional atomic crystal |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103692763A (en) * | 2013-12-06 | 2014-04-02 | 深圳先进技术研究院 | Peeling method of two-dimensional layered nano material |
| CN104973593A (en) * | 2015-06-18 | 2015-10-14 | 湖南大学 | Stripping method of stratified materials |
| CN105506742A (en) * | 2015-12-11 | 2016-04-20 | 山东大学 | Orthorhombic-phase two-dimension-layered SiP2 single-crystal thin film, and preparation method and application thereof |
| CN108611684A (en) * | 2018-04-27 | 2018-10-02 | 清华-伯克利深圳学院筹备办公室 | A kind of controllable thining method of Transition-metal dichalcogenide two-dimensional atomic crystal |
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