CN115652276A - Preparation method of metallic transition metal chalcogenide thin film - Google Patents
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Abstract
The invention relates to a preparation method of a metallic transition metal chalcogenide film, belonging to the technical field of nano material preparation. VB group transition metal elements (such as V, nb or Ta) are introduced into the CVD growth process of the two-dimensional semiconductor type transition metal chalcogenide binary alloy film, and the proportion between the VB group transition metal elements and the VIB group transition metal elements is regulated to generate the two-dimensional metal type transition metal chalcogenide ternary alloy film which is more stable in the air. The preparation method can effectively solve the problem of insufficient source powder vapor caused by low saturated vapor pressure of VB group transition metal oxide source powder in the preparation process of the two-dimensional metallic binary alloy film, changes the growth of the binary film into the growth of a ternary film, and ensures the sufficiency of the source powder vapor in the growth process of the metallic ternary alloy film by utilizing the characteristic of high saturated vapor pressure of VIB group transition metal oxide, thereby realizing the easy preparation of the metallic transition metal chalcogenide film material.
Description
Technical Field
The invention relates to a preparation method of a metallic transition metal chalcogenide film, belonging to the technical field of nano material preparation.
Background
It is known to use molybdenum disulphide (MoS) 2 ) A semiconductive two-dimensional transition metal chalcogenide (MX may be used as the chalcogen) 2 Where M = W, mo, belongs to group VIB; x = S, se, te) as the channel material of the field effect transistor, can effectively avoid the short channel effect, meets the requirements of small volume and high integration of modern integrated circuits, and has wide application prospect in the post-Moore age. When a two-dimensional electronic device based on a two-dimensional transition metal chalcogenide semiconductor material is prepared, a block metal electrode is evaporated in a traditional thermal evaporation mode, high contact resistance is usually formed at an interface, the performance of the device is reduced, and the application of the device is severely limited. Researches show that the contact resistance can be effectively reduced and the device performance can be improved by using a two-dimensional metallic transition metal chalcogenide material to replace a metal block material as an electrode. Therefore, the realization of large-area, large-size, high-efficiency, high-quality and controllable preparation of the two-dimensional metallic transition metal chalcogenide material has very important significance for the application of two-dimensional electronic devices.
Two-dimensional metallic transition metal chalcogenide ((MX) 2 Where M = V, nb, ta, belongs to group VB; x = S, se, te)) material mainly comprises niobium disulfide (NbS) 2 ) Niobium diselenide (NbSe) 2 ) Tantalum disulfide (TaS) 2 ) Titanium diselenide (TiSe) 2 ) And the like. The transition metal element is from group VB. The preparation of these materials has been achieved mainly by "top-down" mechanical or chemical stripping methods and "bottom-up" chemical synthesis methods. Among them, chemical Vapor Deposition (CVD) is more advantageous in the controlled production of two-dimensional materials.
It has been found through investigation of prior art documents that a portion of two-dimensional metallic transition metal chalcogenide thin films have been successively and successfully prepared by CVD. The subject group of university of south African science of Singapore Liu Zheng in Nature Communications 2017, volume 8, page 394 reports niobium oxide (NbO) x X is less than or equal to 2.5) and selenium powder (Se) as a precursor and sodium chloride (NaCl) as an auxiliary growth materialMaterial, synthesizing niobium diselenide (NbSe) by CVD method 2 ) The films, the partially oxidized niobium oxide they use, are obtained by burning Nb powder in advance, the whole growth process has many steps and the operation is complicated. In 2020, the project group Liu Kai of Qinghua university college of materials 5363, ACS Nano 2020, vol.14, pp.175-184 reports using NbCl 5 As Nb source powder, in single layer MoS 2 Upper epitaxially grows NbS 2 A film. NbS 2 The film is unstable in air and is easily oxidized. Therefore, when used as an electrode to construct an optoelectronic device, the performance of the device is affected, which hinders the practical application of the device.
In the preparation process of the metallic two-dimensional transition metal chalcogenide binary alloy film, oxides of VB group transition metals are usually needed to be used as transition metal source powder, the melting points of the oxides are particularly high, and the saturated steam pressure is low, so that the growth temperature of the two-dimensional metallic transition metal chalcogenide binary alloy film is high, and the source powder steam is not sufficiently supplied, thereby causing the shape of the film single crystal to be uncontrollable, and difficult to realize the large-scale and large-size growth of the film. In addition, when chlorides of transition metal elements are used as source powder, the chlorides are more active and are very easily oxidized in the air to become metal oxides, thereby causing the same growth problem. Up to now, the two-dimensional metallic transition metal chalcogenide binary alloy thin film materials successfully prepared by the CVD method are very limited in types, and it is difficult to realize large-scale, large-size, high-quality growth. Moreover, during the process of transferring the two-dimensional metallic transition metal chalcogenide binary alloy thin film material in the air and processing devices, a natural oxide layer with the thickness of several nanometers, such as NbS, can be rapidly generated on the surface of the thin film material 2 Is easy to be oxidized into NbS in air 2 NbOx, which also causes contact problems in device applications and reduces device performance. Furthermore, there is no report on the controllable preparation of metallic two-dimensional transition metal chalcogenide ternary alloy thin films.
Therefore, the finding of the two-dimensional metallic transition metal chalcogenide thin film material which has strong stability, is easy to synthesize, and can be controllably prepared in large area, large size, high efficiency and high quality has very important practical significance.
Disclosure of Invention
[ problem ] to
Aiming at the problems existing in the large-scale preparation of the prior two-dimensional metallic transition metal chalcogenide binary alloy thin film, the invention aims to provide a more stable and easily prepared two-dimensional metallic transition metal chalcogenide, and a controllable preparation method which can realize the large-area, large-size, high-efficiency and high-quality preparation of the material, solve the problems of instability, low preparation efficiency and the like of the two-dimensional metallic transition metal chalcogenide thin film, and provide more choices for a two-dimensional metal electrode material.
In order to solve the problems of instability and difficult large-scale, large-size, high-efficiency and high-quality controllable preparation of the existing two-dimensional metallic transition metal chalcogenide binary alloy film, the invention introduces VB group transition metal elements (such as V, nb or Ta) into the CVD growth process of the two-dimensional semiconducting transition metal chalcogenide binary alloy film to regulate the proportion between the VB group transition metal elements and the VIB group transition metal elements so as to generate the two-dimensional metallic transition metal chalcogenide ternary alloy film which is more stable in the air, and provides a large-scale, large-size, high-efficiency and high-quality controllable preparation method of the two-dimensional metallic transition metal chalcogenide ternary alloy film material. The preparation method can effectively solve the problem of insufficient source powder vapor caused by low saturated vapor pressure of VB group transition metal oxide source powder in the preparation process of the two-dimensional metallic binary alloy film, changes the growth of the binary film into the growth of a ternary film, and ensures the sufficiency of the source powder vapor in the growth process of the metallic ternary alloy film by utilizing the characteristic of high saturated vapor pressure of VIB group transition metal oxide, thereby realizing the easy preparation of the metallic transition metal chalcogenide film material. The preparation method is simple and easy to operate, can easily realize large-scale, large-size, high-efficiency and high-quality controllable preparation like a two-dimensional semiconductor transition metal chalcogenide binary alloy film, and can provide more material choices for two-dimensional metal electrodes.
[ solution ]
The first purpose of the invention is to provide a preparation method of a metallic transition metal chalcogenide film, which comprises the following specific steps: a double-temperature-zone tube furnace is selected as growth equipment, VIB group transition metal element source powder and VB group transition metal element source powder are placed in a high-temperature zone of the tube furnace, and the molar ratio of VIB group transition metal elements to VB group transition metal elements in the two source powders is less than 1:2. Placing chalcogen source powder in a low-temperature region of the tubular furnace; the growth substrate is reversed above the ceramic boat filled with transition metal element (VB group or VIB group) source powder with lower melting point, and is placed at the central position of the high temperature zone along with the ceramic boat.
In one embodiment of the invention, the carrier gas of the tube furnace flows from the low-temperature region to the high-temperature region.
In one embodiment of the invention, the source powders can be vaporized simultaneously and reach the growth substrate surface with the carrier gas.
In one embodiment of the invention, the group VIB transition metal source powder comprises one or more of oxides, chlorides or other group VIB transition metal element-containing compounds of group VIB transition metal elements.
In one embodiment of the invention, the group VB transition metal source powder comprises one or more of oxides, chlorides, or other group VIB transition metal element-containing compounds of group VB transition metal elements.
In one embodiment of the present invention, the chalcogen source powder includes an S source powder and an Se source powder.
In one embodiment of the invention, the high temperature zone where the growth substrate is located is raised to a preset growth temperature and is kept at the temperature until the film is stably grown.
In one embodiment of the present invention, the predetermined growth temperature is 750 to 1100 ℃.
In one embodiment of the invention, the carrier gas comprises one or more of hydrogen, argon, nitrogen.
In one embodiment of the present invention, the carrier gas is a mixed gas of hydrogen and argon or nitrogen.
In one embodiment of the present invention, the carrier gas flow rate is 50-100sccm.
In one embodiment of the invention, the tubes of the tube furnace are flushed at high velocity with carrier gas before the high temperature zone begins to heat up; after the temperature rise is started, the carrier gas flow rate is kept constant.
In one embodiment of the invention, the growth is carried out by raising the temperature only in a high-temperature region located downstream of the gas, so that the alloy thin film grows.
In one embodiment of the invention, the growth substrate comprises a silicon wafer with an oxide layer, a quartz, sapphire or mica substrate.
In one embodiment of the invention, the growth substrate is placed upside down over the source powder of the transition metal element having the higher melting point.
In one embodiment of the invention, the duration of the incubation is 10 to 25 minutes.
In one embodiment of the invention, the preparation method adopts a double-temperature-zone tube furnace as chemical vapor deposition equipment for growth, and a tube in a reaction cavity of the tube furnace is a ceramic tube with the diameter of 5cm; selection of MoO 3 Powder, nb 2 O 5 The powder and S powder are respectively used as Mo source, nb source and S source, the source powder powders are respectively placed in a ceramic boat, and Nb source and S source are respectively placed in the ceramic boat 2 O 5 The powder is placed in the center of a high-temperature zone downstream of the gas flow of the tube furnace, and MoO 3 The powder is placed upstream of the gas stream, and Nb 2 O 5 The powder was located 10cm from the place where the S powder was placed upstream of the airflow, with respect to the MoO 3 The positions of the powder are 42cm apart; nitrogen containing 5% hydrogen is used as carrier gas in the whole preparation process; before the temperature control program is started, firstly washing out the air in the tube in a washing mode, then keeping the flow rate of the air flow at 50sccm until the growth end tube furnace is naturally cooled to room temperature to prepare the single-layer metallic Nb x Mo 1-x S 2 A ternary alloy thin film.
The invention utilizes the metallic transition metal chalcogenide thin film prepared by the method.
The second object of the present invention is to utilize the above-mentioned metallic transition metal chalcogenide thin film in the field of electronic device processing.
[ advantageous effects ]:
1. the operation is simple. The invention is carried out on the basis of the existing technology for preparing a two-dimensional semiconductor transition metal chalcogenide binary alloy film by a relatively mature CVD method, the distances between source powders are adjusted according to the melting point difference of the selected source powders, the relative positions of the source powders in a tube furnace are adjusted, the source powders can be ensured to be simultaneously evaporated when the temperature of a high-temperature region of the tube furnace reaches a preset growth temperature, and then the source powders simultaneously reach a growth substrate under the help of carrier gas. In the growth process, only the high-temperature area positioned at the downstream of the gas is heated, and the source powder placed in other areas is heated by the heat radiation of the high-temperature area. If the chalcogen source powder is close to the high-temperature region, the chalcogen source powder is melted before the high-temperature region reaches the preset growth temperature, so that the transition metal source powder is vulcanized or selenized in advance, the continuous evaporation of the source powder is prevented, and the alloy thin film cannot successfully grow on the substrate or form a large-size thin film; if the distance is too far, when the transition metal chalcogen source powder reaches the growth substrate, the chalcogen source powder is not evaporated, and the alloy thin film cannot grow on the substrate, so that the requirement on equipment is low, and the method is easy to implement.
2. The sample cleanliness is high. The ternary alloy film obtained can show metallicity by doping a lower proportion of VB group transition metal elements. Therefore, naCl does not need to be used as an auxiliary growth material to increase the amount of the source powder vapor of the VB group transition metal element, and unnecessary impurities are prevented from being introduced.
3. The sample size is large. The side length of a triangular single crystal film sample can reach hundreds of micrometers, and the side length is larger than the size of a metallic transition metal chalcogenide film commonly reported in the existing literature.
4. Easy to realize large-scale, high-efficiency and controllable preparation. The defects that VB group transition metal element source powder is difficult to evaporate and the saturated vapor pressure is high in the preparation process of the metallic transition metal chalcogenide binary alloy film can be overcome, and the large-range high-efficiency controllable preparation of the metallic ternary alloy film can be easily realized.
5. The stability of the sample in air is strong. Compared with the binary alloy films of the same type, the prepared two-dimensional metallic transition metal chalcogenide ternary alloy film has the advantages that the atomic number of the VB group transition metal element exposed on the surface of the film is greatly reduced, so that the two-dimensional metallic transition metal chalcogenide ternary alloy film is higher in stability in air and can be stored for a longer time.
Drawings
FIG. 1 is a two-dimensional metallic Nb growth on a silicon dioxide substrate of example 1 x Mo 1-x S 2 Light mirror image of ternary alloy film
FIG. 2 shows example 1Nb x Mo 1-x S 2 Raman (Raman) spectrogram of ternary alloy film
FIG. 3 shows example 1Nb x Mo 1-x S 2 Fluorescence (PL) spectrum of ternary alloy film
FIG. 4 shows example 1Nb x Mo 1-x S 2 X-ray photoelectron spectroscopy (XPS) map of ternary alloy thin film
FIG. 5 is example 4NbS 2 Optical mirror image of binary alloy thin film
Detailed Description
The technical solution of the present invention will be further described with reference to the following examples and drawings, but the present invention is by no means limited to the examples.
Example 1
Processing a growth substrate: sequentially carrying out ultrasonic treatment on a silicon dioxide/silicon (SiO 2/Si) substrate by using acetone, absolute ethyl alcohol and deionized water for 10 minutes respectively, and finally blowing the substrate by using high-purity nitrogen for later use.
And (3) growth control: a double-temperature-zone tube furnace is adopted as chemical vapor deposition equipment for growth, and a tube in a reaction cavity of the tube furnace is a ceramic tube with the diameter of 5cm. Selection of MoO 3 Powder (3 mg), nb 2 O 5 Powder (10 mg) and S powder (30 mg) were used as a Mo source, a Nb source and an S source, respectively. These source powder powders were placed in respective ceramic boats. Nb 2 O 5 The powder is placed in the center of a high temperature zone downstream of the gas flow of the tube furnace, moO 3 The powder is placed upstream of the gas flow,and Nb 2 O 5 The powder was located 10cm apart. S powder is placed at the upstream of the air flow and is mixed with MoO 3 The powder was located 42cm apart. Nitrogen containing 5% hydrogen was used as the carrier gas throughout the preparation. Before the temperature control program is started, the air in the tube is flushed out in a flushing mode, and then the flow rate of the gas flow is kept at 50sccm until the temperature of the tube furnace is naturally reduced to the room temperature after the growth is finished.
Starting only Nb during the whole growth process 2 O 5 The temperature zone of the powder was first raised from room temperature to 850 ℃ in a tube furnace high temperature zone and then held for 10 minutes. And then the temperature control procedure is finished, and the tube furnace is naturally cooled to the room temperature.
By the above growth process, in SiO 2 The large-range large-area uniform single-layer metallic Nb is prepared on the Si substrate x Mo 1-x S 2 A ternary alloy thin film.
FIG. 1 shows a light mirror image of the sample prepared, from which it can be seen that the film has a very uniform optical contrast, indicating a uniform number of layers. The sample is mostly triangular and is a single crystal, and the maximum size of the sample can reach 200 mu m.
Fig. 2 shows a raman spectrum of the prepared sample. As can be seen from the figure, nb x Mo 1-x S 2 Several main Raman peaks of the ternary alloy film are respectively positioned at 186.3cm -1 ，224.4cm -1 ，301.4cm -1 ，350.1，382.8cm -1 ，403.3cm -1 Also has MoS 2 And NbS 2 Indicating that the sample prepared is Nb x Mo 1-x S 2 And (3) an alloy film.
FIG. 3 shows Nb prepared x Mo 1-x S 2 (x = 0.2) fluorescence emission spectrum of the alloy thin film sample. It can be seen from the figure that when X =0.2, the sample has no fluorescence signal, and the theoretical calculation indicates that the sample is metallic.
Fig. 4 shows XPS plots of the resulting samples. As can be seen from the figure, the sample contains Nb, mo and S elements, and corresponds to Nb x Mo 1-x S 2 Ternary alloy film characteristics.
Example 2 referring to example 1, nb in step growth control was changed 2 O 5 The amount of powder was 1mg, and the remaining conditions were unchanged, but the resulting film was not metallic.
Example 3 referring to example 1, 850 ℃ in temperature control was changed to 950 ℃, and the remaining conditions were not changed.
Example 4 varying MoO in step growth control with reference to example 1 3 The amount of powder was 0mg, with the remainder of the conditions unchanged, to produce NbS 2 The film is irregular in shape and cannot achieve extensive growth on the substrate. FIG. 5 shows the resulting NbS 2 Light mirror image of the sample.
Claims (10)
1. A preparation method of a metallic transition metal chalcogenide film is characterized by comprising the following specific steps: selecting a double-temperature-zone tube furnace as growth equipment, placing VIB group transition metal element source powder and VB group transition metal element source powder in a high-temperature zone of the tube furnace, and placing chalcogen element source powder in a low-temperature zone of the tube furnace; the growth substrate is reversely buckled above the ceramic boat filled with transition metal element (VB group or VIB group) source powder with a lower melting point and is placed at the central position of the high-temperature zone along with the ceramic boat;
the molar ratio of the VIB group transition metal element to the VB group transition metal element is less than 1:2.
2. The method of claim 1, wherein the carrier gas of the tube furnace flows from the low temperature zone to the high temperature zone.
3. The method according to claim 1, wherein the group VIB transition metal source powder comprises one or more of oxides, chlorides or other group VIB transition metal element-containing compounds of the group VIB transition metal elements.
4. The method of claim 1, wherein the group VB transition metal source powder comprises one or more of an oxide, a chloride or other group VIB transition metal element-containing compound of a group VB transition metal element.
5. The method of claim 1, wherein the chalcogen source powder comprises an S source powder and an Se source powder.
6. The method according to claim 1, wherein the high temperature zone in which the growth substrate is located is raised to a preset growth temperature and kept at the preset growth temperature until the film is stably grown; the preset growth temperature is 750-1100 ℃.
7. The method of claim 1, wherein the carrier gas comprises one or more of hydrogen, argon, nitrogen; the carrier gas flow rate is 50-100sccm.
8. The method of claim 1, wherein the growth substrate comprises a silicon wafer with an oxide layer, a quartz, sapphire, or mica substrate.
9. A metallic transition metal chalcogenide thin film produced by the method of any one of claims 1 to 8.
10. Use of the metallic transition metal chalcogenide thin film of claim 9 in the field of electronic device processing.
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