CN113410287B - Two-dimensional SnSe-SnSe 2 P-n heterojunction and preparation method thereof - Google Patents
Two-dimensional SnSe-SnSe 2 P-n heterojunction and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of nano semiconductor materials, and particularly discloses two-dimensional SnSe-SnSe 2 The p-n heterojunction and the preparation method thereof comprise the following steps: s1, mixing stannous iodide and selenium powder to obtain a precursor, and heating the precursor to generate SnSe 2 Crystal material, introducing carrier gas to make said SnSe 2 The crystal material is taken to the substrate and is deposited on the substrate to form two-dimensional SnSe 2 A crystalline material; s2 converting the two-dimensional SnSe 2 Heating the crystal material to partially decompose the crystal material at high temperature in situ to obtain SnSe-SnSe 2 A p-n heterojunction. The invention can reduce the reaction temperature, reduce the energy consumption in the preparation process, simultaneously overcome the difficult problems of wet chemistry and mechanical synthesis, and realize the controllable preparation of the two-dimensional layered material.
Description
Technical Field
The invention belongs to the field of nano semiconductor materials, and particularly relates to two-dimensional SnSe-SnSe 2 A p-n heterojunction and a method for making the same.
Background
Since the first successful preparation of graphene by mechanical exfoliation in 2004 by geom and Novoselov, two-dimensional materials have attracted much attention as a new functional material. Although graphene has ultrahigh electron mobility and good ductility, its zero band gap property limits its application in optoelectronic and electronic devices, and for this field, the ideal material is a two-dimensional semiconductor. To date, a large number of graphene-like ultrathin two-dimensional nanomaterials have been prepared by various methods in addition to graphene, but the current research is mainly based on a two-dimensional n-type semiconductor material, and a two-dimensional p-type semiconductor stably existing at room temperature is lacked, thereby seriously affecting the development of a two-dimensional p-n heterojunction.
SnSe 2 And SnSe is a two-dimensional material consisting of the same metal atoms (Sn) and chalcogen atoms (Se), and has the advantages of low cost, rich element reserves, environmental friendliness and the like compared with transition metal chalcogen compounds. In addition, they also have a rich electronic band structure and carrier type: snSe 2 Has a sum of MoS 2 A similar hexagonal layered structure, belonging to an electron-dominated n-type semiconductor; snSe has the similarity with black phosphorusThe structure of the orthorhombic system is that one Sn atom is connected with three Se atoms to form a wrinkled Sn-Se layer, the layers are combined by Van der Waals force to form a two-dimensional layered structure, and the formation enthalpy of Sn vacancies is small in the coordination process so that a shallow acceptor level is easily formed, and SnSe shows the property of a p-type semiconductor with a dominant hole. More importantly, p-SnSe and n-SnSe 2 The method is used for constructing the intrinsic p-n heterojunction, can effectively avoid performance reduction caused by diffusion of hetero atoms in a junction region, and is expected to construct a high-performance two-dimensional p-n heterojunction photodetector.
In recent years, two-dimensional SnSe 2 And SnSe are gradually drawing attention from researchers: for example, snCl is adopted by Mark T. Swihart subject group of Buffalo university 2 And a selenium source are subjected to liquid phase synthesis in an organic solvent environment to form ultrathin SnSe nanosheets; the Gao Hongjun of the institute of physics of the Chinese academy of sciences and the Liu Zheng task group of the southern oceanic university of Singapore were mechanically stripped to obtain a few-layer SnSe 2 And a high-performance field effect transistor and a photodetector are constructed. However, both of these preparation methods have their limitations: the sample synthesized by the liquid phase method has inevitable residual impurities such as organic solvent on the surface, which seriously damages the performance of the device; although the nanosheet obtained by the mechanical stripping method has high crystalline quality, the size and the thickness of the product are uncontrollable, the yield is very small, and large-scale uniform preparation is difficult to realize. The vapor deposition method is an effective means for efficiently synthesizing two-dimensional materials, and at present, a metal source (SnO) with high melting point is mostly adopted 2 And SnSe) as a raw material, so that the concentration difference between the raw materials is large in the reaction process, and the synthesized nanosheet is generally thick. Compared with SnSe 2 In addition, snSe has larger interlayer acting force, and the difficulty of obtaining the two-dimensional structure by a gas phase method is higher, so the research work of the two-dimensional structure is relatively less, and the two-dimensional SnSe-SnSe is caused 2 The fabrication of p-n heterojunctions has progressed slowly.
Disclosure of Invention
In view of the above-identified deficiencies or needs in the art, the present invention provides a two-dimensional SnSe-SnSe 2 The p-n heterojunction and the preparation method thereof aim at adopting stannous iodide and selenium powder which are easy to react as a metal source and a selenium source,the reaction zone is spatially isolated from the deposition zone, so that the reaction temperature can be correspondingly reduced, the substrate is prevented from being damaged, and the two-dimensional SnSe is obtained 2 After the crystal material is crystallized, the crystal material is heated to partially convert the crystal material into SnSe, thereby obtaining two-dimensional SnSe-SnSe 2 The p-n heterojunction crystalline material overcomes the difficult problems of wet chemistry and mechanical synthesis, and realizes the controllable preparation of the two-dimensional layered material.
To achieve the above object, according to one aspect of the present invention, there is provided a two-dimensional SnSe-SnSe 2 The preparation method of the p-n heterojunction comprises the following steps:
s1, mixing stannous iodide and selenium powder to obtain a precursor, and heating the precursor to generate SnSe 2 Crystal material, introducing carrier gas to make said SnSe 2 The crystal material is taken to the substrate and is deposited on the substrate to form two-dimensional SnSe 2 A crystalline material;
s2 combining the two-dimensional SnSe 2 Heating the crystal material to partially decompose the crystal material at high temperature in situ to obtain SnSe-SnSe 2 p-n heterojunction to complete SnSe-SnSe 2 And preparing a p-n heterojunction.
Preferably, the step S1 and the step S2 are both carried out in a tube furnace, and the tube furnace is divided into an upstream low-temperature area, a central temperature area and a downstream deposition area in sequence; in the S1, the precursor is arranged in an upstream low-temperature region, and the substrate is arranged in a downstream deposition region; in S2, the two-dimensional SnSe 2 The crystalline material is placed in the central temperature zone.
More preferably, in S1, the central temperature zone is heated at a rate of 30 ℃ per minute, and the temperature of the central temperature zone is controlled to be 550 ℃ to 650 ℃.
As further preferred, the SnSe 2 When the crystal material is deposited on the substrate, the temperature of the downstream deposition area where the crystal material is located is 200-300 ℃.
It is further preferred that the pressure in the central temperature zone and the downstream deposition zone in S1 and S2 is not greater than one atmosphere.
More preferably, the carrier gas is argon gas and hydrogen gas, and the flow rate of argon gas is 20sccm and the flow rate of hydrogen gas is 5sccm.
More preferably, in S2, the central temperature zone is heated at a rate of 30 ℃ per minute, and the temperature of the central temperature zone is controlled to be 300 ℃ to 400 ℃.
More preferably, the reaction time in S2 is 5 to 30min.
As a further preferred, the substrate is mica.
According to another aspect of the present invention, there is provided the above two-dimensional SnSe-SnSe 2 A p-n heterojunction, which is prepared by the method.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. the precursors of the invention are low-melting-point stannous iodide and selenium powder, which can ensure that the evaporation rates of the two precursors are close to each other, and the stannous iodide and selenium powder which are easy to react are used as a metal source and a selenium source, thereby effectively reducing the reaction freedom, simplifying the reaction and being easy to occur, reducing the temperature of a central temperature region, and further reducing the energy consumption in the preparation process.
2. The substrate is arranged in the downstream deposition area and keeps a certain distance from the central temperature area, so that the damage to the substrate caused by overhigh temperature of the central temperature area can be avoided, and the two-dimensional SnSe-SnSe prepared by the method provided by the invention 2 The p-n heterojunction crystalline material can overcome the difficult problems of wet chemistry and mechanical synthesis, and realize the controllable preparation of the two-dimensional layered material.
3. The two-dimensional SnSe obtained by the first step reaction 2 Crystal material ultrathin SnSe 2 Heating the nano-sheet crystal material to ensure that Sn-Se on the surface of the nano-sheet crystal material is broken and subjected to phase change so as to form an ultrathin SnSe nano-sheet crystal material in situ, and accurately controlling the reaction temperature and time to obtain two-dimensional SnSe-SnSe 2 A p-n heterocrystalline material.
4. The invention adopts a rapid heating method to carry out heating on ultrathin SnSe 2 The nanosheet crystal material is heated, so that residual reaction in the processes of heating and cooling can be effectively prevented from continuing; at the same time, due to the temperature of the central temperature zoneToo high of a concentration may result in ultra-thin SnSe 2 The nano-sheet crystal material is directly volatilized at an excessively high decomposition rate, so that the SnSe crystal material is not favorably obtained, and the energy barrier of Sn-Se bond fracture cannot be reached when the temperature of a central temperature zone is excessively low, so that the phase change reaction cannot be carried out.
5. The invention also optimizes the pressure, the type of carrier gas and the flow rate of the carrier gas, and can obtain the two-dimensional SnSe-SnSe with smooth surface, uniform Sn and Se distribution and mostly regular triangle appearance by the combined action of the conditions 2 A p-n heterocrystalline material.
Drawings
FIG. 1 is a two-dimensional SnSe-SnSe of an embodiment of the present invention 2 Schematic preparation process of the p-n heterojunction crystalline material;
FIGS. 2a to 2c are two-dimensional SnSe prepared in examples 1 to 3 of the present invention 2 A topographical top view of the crystalline material;
FIGS. 3a and 3b are two-dimensional SnSe-SnSe prepared by the method of example 4 2 Surface topography map and phase characterization map of the p-n heterojunction;
FIGS. 4a and 4b are two-dimensional SnSe-SnSe prepared by the method of example 5 2 Surface topography map and phase characterization map of the p-n heterojunction;
FIGS. 5a to 5c are two-dimensional SnSe-SnSe prepared by the method of example 4 of the present invention 2 Crystal structure, raman spectrum and thickness measurement diagram of p-n heterojunction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The embodiment of the invention provides two-dimensional SnSe-SnSe 2 A method for preparing a p-n heterojunction, in particular using a tube furnace, which method comprisesThe tube furnace is sequentially divided into an upstream low-temperature area, a central temperature area and a downstream deposition area, as shown in figure 1, and comprises the following steps:
s1, mixing stannous iodide and selenium powder to obtain a precursor, placing the precursor in an upstream low-temperature region, heating the central temperature region, and reacting the precursor to generate SnSe 2 Crystal material, introducing carrier gas to make said SnSe 2 The crystalline material is carried to a downstream deposition zone and deposited on a mica substrate located in the downstream deposition zone to form two-dimensional SnSe 2 A crystalline material;
s2 combining the two-dimensional SnSe 2 The crystal material is arranged in a central temperature zone, argon is introduced into the central temperature zone, and the central temperature zone is heated to ensure that the two-dimensional SnSe is obtained 2 The crystal material is decomposed and converted into SnSe under high temperature, namely Sn-Se on the surface of the crystal material is cracked and subjected to phase change so as to form an ultrathin SnSe nanosheet crystal material in situ, and thus two-dimensional SnSe-SnSe nanosheet crystal material is obtained in situ 2 p-n heterojunction to complete SnSe-SnSe 2 And preparing a p-n heterojunction.
Further, in the step S1, the central temperature zone is heated at a rate of 30 ℃ per minute, the temperature of the central temperature zone is controlled to 550 ℃ to 650 ℃, preferably 600 ℃, and the SnSe is allowed to react 2 When the crystal material is deposited on the substrate, the temperature of a downstream deposition area where the crystal material is located is 200-300 ℃; the carrier gas is pure argon and hydrogen, the flow rate of the argon is 20sccm, and the flow rate of the hydrogen is 5sccm.
Further, in S2, before reaction, a reaction area is pre-vacuumized, then argon is filled, gas is repeatedly washed until air is exhausted, and argon with the flow of 100 sccm-200 sccm is filled during reaction; two-dimensional SnSe by adopting rapid heating method 2 Heating the crystal material, specifically heating a central temperature zone at a speed of 30 ℃ per minute, and controlling the temperature of the central temperature zone to be 300-400 ℃, and further preferably 370 ℃; the reaction time is 5 min-30 min.
Further, in the S1 and the S2, the pressure of the central temperature area and the pressure of the downstream deposition area are controlled to be not more than one atmosphere.
Two-dimensional SnSe-SnSe prepared by adopting the method 2 Heterogeneous p-nThe shape of the junction is mostly regular triangle, and the thickness is less than 5nm.
The following are specific examples:
example 1
A single-temperature-zone horizontal tube furnace is adopted as a reaction device, the tube length of the horizontal tube furnace is 90cm, the outer diameter of the horizontal tube furnace is 25mm, the tube wall thickness is 2mm, the range of a constant-temperature zone is 10cm, the temperature of a central temperature zone is 550 ℃, the temperature of a downstream deposition zone is 200 ℃, and the heating rate is 30 ℃/min; by SnI 2 And Se powder (purity)>99.99%) as Sn and Se sources, placed in an upstream low-temperature region; adopting fluorophlogopite sheet as a substrate to be placed at a position 16cm away from a central temperature area at the downstream; before the reaction, pre-vacuumizing to about 10Pa, then filling Ar of 600sccm to atmospheric pressure, and repeatedly washing gas to remove residual oxygen; ar of 20sccm and H of 5sccm are introduced in the reaction process 2 As carrier gas, keeping the pressure at one atmospheric pressure, reacting for 10 minutes, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with the furnace, and obtaining two-dimensional SnSe from fluorophlogopite sheet 2 A crystalline material.
Example 2
A single-temperature-zone horizontal tube furnace is adopted as a reaction device, the tube length of the horizontal tube furnace is 90cm, the outer diameter of the horizontal tube furnace is 25mm, the tube wall thickness is 2mm, the range of a constant-temperature zone is 10cm, the temperature of a central temperature zone is 600 ℃, the temperature of a downstream deposition zone is 200 ℃, and the heating rate is 30 ℃/min; by SnI 2 And Se powder (purity)>99.99%) as Sn and Se sources, placed in an upstream low-temperature region; adopting fluorophlogopite sheet as a substrate and placing the substrate at a position 16cm away from the central temperature area at the downstream; before the reaction, pre-vacuumizing to about 10Pa, then filling Ar of 600sccm to atmospheric pressure, and repeatedly washing gas to remove residual oxygen; introducing Ar of 20sccm and H of 5sccm in the reaction process 2 As carrier gas, keeping the pressure at one atmospheric pressure, reacting for 10 minutes, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with the furnace, and obtaining two-dimensional SnSe from fluorophlogopite sheet 2 A crystalline material.
Example 3
A single-temperature-zone horizontal tube furnace is adopted as a reaction device, the tube length of the horizontal tube furnace is 90cm, and the outer diameter is 25mm, the thickness of the tube wall is 2mm, the range of a constant temperature area is 10cm, the temperature of a central temperature area is 650 ℃, the temperature of a downstream deposition area is 200 ℃, and the heating rate is 30 ℃/min; by SnI 2 And Se powder (purity)>99.99%) as a source of Sn and Se placed in an upstream low temperature zone; adopting fluorophlogopite sheet as a substrate to be placed at a position 16cm away from a central temperature area at the downstream; before the reaction, pre-vacuumizing to about 10Pa, then filling Ar of 600sccm to atmospheric pressure, and repeatedly washing gas to remove residual oxygen; ar of 20sccm and H of 5sccm are introduced in the reaction process 2 As carrier gas, keeping the pressure at one atmospheric pressure, reacting for 10 minutes, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with the furnace, and obtaining two-dimensional SnSe from fluorophlogopite sheet 2 A crystalline material.
Example 4
A single-temperature-zone horizontal tube furnace is adopted as a reaction device, the tube length of the horizontal tube furnace is 90cm, the outer diameter of the horizontal tube furnace is 25mm, the tube wall thickness is 2mm, the range of a constant temperature zone is 10cm, and the SnSe prepared in the embodiment 2 is 2 The crystal material is placed in a central temperature zone, the temperature is 350 ℃, and the heating rate is 30 ℃/min; before the reaction, pre-vacuumizing to about 10Pa, then filling Ar of 600sccm to atmospheric pressure, and repeatedly washing gas to remove residual oxygen; introducing 100sccm Ar as a carrier gas in the reaction process, keeping the pressure at one atmospheric pressure, reacting for 10 minutes, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with the furnace, and obtaining the two-dimensional SnSe-SnSe from the fluorophlogopite sheet 2 A heterocrystalline material.
Example 5
A single-temperature-zone horizontal tube furnace with a tube length of 90cm, an outer diameter of 25mm, a tube wall thickness of 2mm and a constant temperature zone range of 10cm was used as a reaction device, and the SnSe obtained in example 2 was used 2 The crystal material is placed in a central temperature zone, the temperature is 420 ℃, and the heating rate is 30 ℃/min; before the reaction, pre-vacuumizing to about 10Pa, then filling Ar of 600sccm to atmospheric pressure, and repeatedly washing gas to remove residual oxygen; introducing 100sccm Ar as carrier gas during the reaction process, maintaining the pressure at one atmospheric pressure, reacting for 10 minutes, keeping the carrier gas unchanged after the reaction is finished, cooling the product to room temperature along with the furnace, and cooling the product to room temperatureSnSe obtained on fluorophlogopite sheet 2 Complete phase transformation into SnSe, but the temperature is too high, so that the decomposition degree of SnSe seriously appears etching.
Two-dimensional SnSe of pure phase prepared in examples 1-3 was analyzed by optical microscope 2 The morphology of the crystal material is characterized, the results are shown in fig. 2 a-2 c, and it can be seen from fig. 2 a-2 c that the two-dimensional SnSe is obtained when the temperature is increased from 550 ℃ to 650 DEG C 2 The size of the crystalline material becomes smaller from small to large, so that the two-dimensional SnSe synthesized in example 2 2 Crystalline materials are suitable.
Two-dimensional SnSe-SnSe prepared in examples 4 to 5 were subjected to an optical microscope and a confocal Raman microscope 2 And (3) carrying out surface morphology and phase characterization on the heterojunction crystal material. As shown in FIGS. 3a and 3b, the sample obtained in example 4 was SnSe 2 Partially converted into a nanosheet structure of SnSe; when SnSe is present as shown in FIG. 4a and FIG. 4b 2 SnSe too high when the decomposition temperature rises to 400 DEG C 2 The decomposition speed is too fast to control, which causes the whole phase of the material to be transformed into SnSe and serious etching phenomenon to occur.
Two-dimensional SnSe-SnSe prepared in example 4 is subjected to transmission electron microscopy and confocal Raman microscopy 2 Characterization of the crystal structure of the heterocrystal material, as shown in fig. 5a to 5c, it can be seen that the material prepared in example 4 is SnSe and SnSe 2 A co-existing heterocrystalline material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. Two-dimensional SnSe-SnSe 2 The preparation method of the p-n heterojunction is characterized by comprising the following steps:
s1, mixing stannous iodide and selenium powder to obtain a precursor, and heating the precursor to generate SnSe 2 Crystal material, introducing carrier gas to make said SnSe 2 Crystalline material is brought to the linerAt the bottom, depositing it on the substrate to form two-dimensional SnSe 2 A crystalline material;
s2 combining the two-dimensional SnSe 2 Heating the crystal material to partially decompose the crystal material at high temperature to obtain SnSe-SnSe in situ 2 p-n heterojunction to complete SnSe-SnSe 2 preparing a p-n heterojunction;
the step S1 and the step S2 are both carried out in a tube furnace, and the tube furnace is sequentially divided into an upstream low-temperature area, a central temperature area and a downstream deposition area; in the S1, the precursor is arranged in an upstream low-temperature region, the substrate is arranged in a downstream deposition region, a central temperature region is heated at a speed of 30 ℃ per minute, and the temperature of the central temperature region is controlled to be 550-650 ℃; in S2, the two-dimensional SnSe 2 The crystal material is placed in a central temperature zone, the central temperature zone is heated at the speed of 30 ℃ per minute, and the temperature of the central temperature zone is controlled to be 300-400 ℃; prepared SnSe-SnSe 2 The thickness of the p-n heterojunction is less than 5nm.
2. The two-dimensional SnSe-SnSe of claim 1 2 A method for preparing a p-n heterojunction, characterized in that the SnSe is 2 When the crystal material is deposited on the substrate, the temperature of the downstream deposition area where the crystal material is located is 200-300 ℃.
3. The two-dimensional SnSe-SnSe of claim 1 2 The preparation method of the p-n heterojunction is characterized in that in the S1 and the S2, the pressure of a central temperature area and the pressure of a downstream deposition area are not more than one atmosphere.
4. The two-dimensional SnSe-SnSe of claim 1 2 The preparation method of the p-n heterojunction is characterized in that the carrier gas is argon and hydrogen, the flow rate of the argon is 20sccm, and the flow rate of the hydrogen is 5sccm.
5. The two-dimensional SnSe-SnSe of claim 1 2 The preparation method of the p-n heterojunction is characterized in that in the S2, the reaction time is 5-30 min.
6. The two-dimensional SnSe-SnSe of any one of claims 1 to 5 2 A method of making a p-n heterojunction, wherein said substrate is mica.
7. Two-dimensional SnSe-SnSe 2 A p-n heterojunction produced by the method according to any one of claims 1 to 6.
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