CN113410287A - Two-dimensional SnSe-SnSe2P-n heterojunction and preparation method thereof - Google Patents
Two-dimensional SnSe-SnSe2P-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-SnSe2The p-n heterojunction and the preparation method thereof comprise the following steps: s1 mixing stannous iodide and selenium powder to obtain precursor, heating the precursor to generate SnSe2Crystal material, introducing carrier gas to make said SnSe2The crystal material is taken to the substrate and is deposited on the substrate to form two-dimensional SnSe2A crystalline material; s2 converting the two-dimensional SnSe2Heating the crystal material to partially decompose the crystal material at high temperature to obtain SnSe-SnSe in situ2A 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-SnSe2A 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 two-dimensional n-type semiconductor materials, and two-dimensional p-type semiconductors stably existing at room temperature are lacked, so that the development of two-dimensional p-n heterojunctions is seriously influenced.
SnSe2And 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: SnSe2Has a sum of MoS2A similar hexagonal layered structure, belonging to an electron-dominated n-type semiconductor; the SnSe has an orthorhombic structure similar to that of black phosphorus, 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, so that the SnSe shows the property of a p-type semiconductor with dominant holes. More importantly, p-SnSe and n-SnSe2The 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 SnSe2And SnSe are gradually drawing attention from researchers: for example, SnCl is adopted by Mark T. Swihart subject group of Buffalo university2And a selenium source are subjected to liquid phase synthesis in an organic solvent environment to form ultrathin SnSe nanosheets; the high-hong Jun of the physical research institute of the Chinese academy and the Liu's topic group of the southern American university of Singapore are mechanically stripped to obtain a few layers of SnSe2And 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 nano-sheet obtained by the mechanical stripping method has high crystalline quality, the product size and the thickness are not equalControllable, and 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 adopted2And 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 SnSe2In 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 caused2The fabrication of p-n heterojunctions has progressed slowly.
Disclosure of Invention
In view of the above-identified deficiencies in the art or needs for improvement, the present invention provides a two-dimensional SnSe-SnSe2The 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, and isolating a reaction area from a deposition area in space, so that the reaction temperature can be correspondingly reduced, the substrate is prevented from being damaged, and the two-dimensional SnSe is obtained2After the crystal material is crystallized, the crystal material is heated to partially convert the crystal material into SnSe, thereby obtaining two-dimensional SnSe-SnSe2The 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-SnSe2The preparation method of the p-n heterojunction comprises the following steps:
s1 mixing stannous iodide and selenium powder to obtain precursor, heating the precursor to generate SnSe2Crystal material, introducing carrier gas to make said SnSe2The crystal material is taken to the substrate and is deposited on the substrate to form two-dimensional SnSe2A crystalline material;
s2 converting the two-dimensional SnSe2Heating the crystal material to partially decompose the crystal material at high temperature to obtain SnSe-SnSe in situ2p-n heterojunction to complete SnSe-SnSe2And preparing a p-n heterojunction.
As a further preference, both of said S1 and S2 are carried out in a tube furnace, which is divided intoAn upstream low temperature zone, a central temperature zone, and a downstream deposition zone; in the step S1, the precursor is placed in an upstream low-temperature zone, and the substrate is placed in a downstream deposition zone; in the S2, the two-dimensional SnSe2The 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 550 ℃ to 650 ℃.
As further preferred, the SnSe2When 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 preferable that the pressure in the central temperature zone and the downstream deposition zone in S1 and S2 is not more than one atmosphere.
Further 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 5 sccm.
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, in S2, the reaction time is 5 to 30 min.
As a further preferred, the substrate is mica.
According to another aspect of the present invention, there is provided the two-dimensional SnSe-SnSe as described above2A 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 invention arranges the substrate in the downstream deposition area, and keeps a certain distance with the central temperature areaThe distance can avoid damaging the substrate due to overhigh temperature of the central temperature zone, so the method for preparing the two-dimensional SnSe-SnSe provided by the invention2The 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 reaction of the first step2Crystal material ultrathin SnSe2Heating the nanosheet crystal material to ensure that Sn-Se on the surface of the nanosheet crystal material is broken and subjected to phase change so as to form an ultrathin SnSe nanosheet crystal material in situ, and accurately controlling the reaction temperature and time to obtain two-dimensional SnSe-SnSe2A p-n heterocrystalline material.
4. The invention adopts a rapid heating method to carry out heating on ultrathin SnSe2The nanosheet crystal material is heated, so that residual reaction in the processes of temperature rise and temperature reduction can be effectively prevented from continuing; meanwhile, the ultra-thin SnSe can be caused by the over-high temperature of the central temperature zone2The 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 conditions2A p-n heterocrystalline material.
Drawings
FIG. 1 is a two-dimensional SnSe-SnSe of an embodiment of the present invention2Schematic 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 invention2A topographical top view of the crystalline material;
FIGS. 3a and 3b are two-dimensional SnSe-SnSe prepared by the method of example 42Surface 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 52Heterogeneous p-nSurface topography map and phase characterization map of the junction;
FIGS. 5a to 5c are two-dimensional SnSe-SnSe prepared by the method of example 4 of the present invention2Crystal 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-SnSe2The preparation method of the p-n heterojunction specifically adopts a tubular furnace for preparation, the tubular furnace is sequentially divided into an upstream low-temperature region, a central temperature region and a downstream deposition region, and as shown in figure 1, the preparation method comprises the following steps:
s1 mixing stannous iodide and selenium powder to obtain precursor, placing the precursor in an upstream low-temperature region, heating the central temperature region to react the precursor to generate SnSe2Crystal material, introducing carrier gas to make said SnSe2The 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 SnSe2A crystalline material;
s2 converting the two-dimensional SnSe2Placing the crystal material in a central temperature zone, introducing argon gas into the central temperature zone, and heating to ensure that the two-dimensional SnSe is formed2The 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 situ2p-n heterojunction to complete SnSe-SnSe2And preparing a p-n heterojunction.
Further, in 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 react2When the crystalline material is deposited on a substrate, itThe temperature of the downstream deposition area 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 5 sccm.
Further, in the step S2, before the reaction, the reaction area is pre-vacuumized, then argon is filled, the gas is repeatedly washed until the air is exhausted, and the argon with the flow rate of 100 sccm-200 sccm is filled during the reaction; two-dimensional SnSe by adopting rapid heating method2Heating 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 S2, the pressure of the central temperature zone and the downstream deposition zone is controlled not to be more than one atmosphere.
Two-dimensional SnSe-SnSe prepared by adopting the method2The p-n heterojunction is mostly regular triangle in shape and is less than 5nm in thickness.
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 SnI2And 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 process2As 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 sheet2A 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 is 25mm, and the thickness of the tube wall2mm, 10cm in constant temperature area, 600 ℃ in central temperature area, 200 ℃ in downstream deposition area and 30 ℃/min in heating rate; by SnI2And 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 process2As 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 sheet2A 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, 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 650 ℃, the temperature of a downstream deposition zone is 200 ℃, and the heating rate is 30 ℃/min; by SnI2And 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 process2As 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 sheet2A crystalline material.
Example 4
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 used2The 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; 100sc is introduced in the reaction processcm Ar is used as carrier gas, the pressure is kept at one atmospheric pressure, the reaction time is 10 minutes, the carrier gas is kept unchanged after the reaction is finished, the product is cooled to room temperature along with the furnace, and two-dimensional SnSe-SnSe is obtained from the fluorophlogopite sheet2A 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 used2The 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, 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 SnSe from fluorophlogopite sheets2Complete phase transformation is converted into SnSe, but the temperature is too high, so that the decomposition degree of the SnSe is seriously etched.
Optical microscopy of pure phase two-dimensional SnSe prepared in examples 1-32The 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 C2The size of the crystalline material becomes smaller from small to large, so that the two-dimensional SnSe synthesized in example 22Crystalline materials are suitable.
Two-dimensional SnSe-SnSe prepared in examples 4 to 5 is subjected to an optical microscope and a confocal Raman microscope2And (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 SnSe2Partially converted into a nanosheet structure of SnSe; when SnSe is present as shown in FIG. 4a and FIG. 4b2SnSe too high when the decomposition temperature rises to 400 DEG C2The 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 microscopy2HeterojunctionThe crystal material is subjected to crystal structure characterization, as shown in fig. 5a to 5c, it can be seen that the material prepared in example 4 is SnSe and SnSe2A 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 (10)
1. Two-dimensional SnSe-SnSe2The preparation method of the p-n heterojunction is characterized by comprising the following steps:
s1 mixing stannous iodide and selenium powder to obtain precursor, heating the precursor to generate SnSe2Crystal material, introducing carrier gas to make said SnSe2The crystal material is taken to the substrate and is deposited on the substrate to form two-dimensional SnSe2A crystalline material;
s2 converting the two-dimensional SnSe2Heating the crystal material to partially decompose the crystal material at high temperature to obtain SnSe-SnSe in situ2p-n heterojunction to complete SnSe-SnSe2And preparing a p-n heterojunction.
2. The two-dimensional SnSe-SnSe of claim 12The preparation method of the p-n heterojunction is characterized in that S1 and S2 are both carried out in a tube furnace, and the tube furnace is sequentially divided into an upstream low-temperature region, a central temperature region and a downstream deposition region; in the step S1, the precursor is placed in an upstream low-temperature zone, and the substrate is placed in a downstream deposition zone; in the S2, the two-dimensional SnSe2The crystalline material is placed in the central temperature zone.
3. The two-dimensional SnSe-SnSe of claim 22The preparation method of the p-n heterojunction is characterized in that in S1, a central temperature zone is heated at a speed of 30 ℃ per minute, and the temperature of the central temperature zone is controlled to be 550-650 ℃.
4. As claimed in claim3 the two-dimensional SnSe-SnSe2A method for preparing a p-n heterojunction, characterized in that the SnSe is2When the crystal material is deposited on the substrate, the temperature of the downstream deposition area where the crystal material is located is 200-300 ℃.
5. The two-dimensional SnSe-SnSe of claim 22The preparation method of the p-n heterojunction is characterized in that in the S1 and the S2, the pressure of the central temperature area and the pressure of the downstream deposition area are not more than one atmosphere.
6. The two-dimensional SnSe-SnSe of claim 12The 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 5 sccm.
7. The two-dimensional SnSe-SnSe of claim 22The preparation method of the p-n heterojunction is characterized in that in S2, a central temperature zone is heated at a speed of 30 ℃ per minute, and the temperature of the central temperature zone is controlled to be 300-400 ℃.
8. The two-dimensional SnSe-SnSe of claim 12The preparation method of the p-n heterojunction is characterized in that in the S2, the reaction time is 5-30 min.
9. The two-dimensional SnSe-SnSe of any one of claims 1 to 82A method of making a p-n heterojunction, wherein said substrate is mica.
10. Two-dimensional SnSe-SnSe2A p-n heterojunction produced by the method according to any one of claims 1 to 9.
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