CN113174583B - Open quartz boat and preparation method of large-area continuous two-dimensional transition metal sulfur compound film - Google Patents

Open quartz boat and preparation method of large-area continuous two-dimensional transition metal sulfur compound film Download PDF

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CN113174583B
CN113174583B CN202110282034.4A CN202110282034A CN113174583B CN 113174583 B CN113174583 B CN 113174583B CN 202110282034 A CN202110282034 A CN 202110282034A CN 113174583 B CN113174583 B CN 113174583B
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quartz boat
transition metal
dimensional transition
heating
precursor
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CN113174583A (en
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杨伟煌
陈相硕
宋佳豪
董林玺
王高峰
周昌杰
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Hangzhou Dianzi University
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Hangzhou Dianzi University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4485—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation without using carrier gas in contact with the source material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber

Abstract

The invention relates to an open quartz boat and a preparation method of a large-area continuous two-dimensional transition metal sulfur compound film, wherein one end of the open quartz boat is provided with an opening, and the preparation method of the large-area continuous two-dimensional transition metal sulfur compound film comprises the following steps: 1) Placing precursor powder at one end of the open quartz boat A, wherein an opening is formed in the quartz boat A; 2) Placing a sulfur source or a selenium source in an open quartz boat B; 3) The substrate soaked with the catalyst solution is reversely buckled above the precursor powder in the open quartz boat A; 4) Placing an opening quartz boat A and an opening quartz boat B in a main furnace heating zone and a preheating heating zone of the tube furnace respectively, wherein the opening ends of the opening quartz boat A and the opening end of the opening quartz boat B are opposite; heating the precursor and the sulfur source or the selenium source in sequence; 6) A two-dimensional transition metal chalcogenide is generated and deposited on the substrate surface. The invention avoids forming turbulent flow when preparing the two-dimensional transition metal sulfur compound film, and is beneficial to obtaining the large-area continuous two-dimensional transition metal sulfur compound film.

Description

Open quartz boat and preparation method of large-area continuous two-dimensional transition metal sulfur compound film
Technical Field
The invention belongs to the field of two-dimensional materials, and particularly relates to a large-opening quartz boat and a preparation method of a large-area continuous two-dimensional transition metal sulfur compound film based on the opening quartz boat.
Background
When conventional semiconductor materials are applied to develop flexible electronic sensors, for example, si can be used to fabricate flexible devices by thinning it below a certain value. However, due to the fragile nature of silicon, it poses a serious threat to the reliability of the device. Other methods, including the use of organic materials to fabricate flexible devices, have also been extensively studied, but these techniques have not been universally applicable due to the inability to solve problems of low carrier mobility, high operating voltage, large leakage current, etc. On the other hand, as the semiconductor technology develops, the feature size of the semiconductor device becomes smaller and smaller, and the device size also faces the 7nm bottleneck at present. As dimensions continue to shrink, more and more difficulties begin to arise, such as short channel effects, which are difficult to overcome, and can significantly degrade the performance of silicon-based devices. There is a strong need for a semiconductor material that can replace silicon.
Since the discovery of graphene, two-dimensional materials have received increasing attention, and due to their excellent properties, are considered to have a great potential to replace silicon as a next-generation revolutionary semiconductor material.
The two-dimensional transition metal chalcogenide (TMDs) is a novel graphene-like nano material, has excellent performances such as good crystallinity, large specific surface area and high absorption coefficient, is linked by strong covalent bonds in the layer, has good stability, and is connected by Van der Waals force between layers, so that the effect between the transition metal chalcogenide layers is easily broken, the transition metal chalcogenide can be easily stripped from multiple layers to a single layer, the band gap of the transition metal chalcogenide is gradually increased along with the reduction of the number of the layers, the single layer is converted into a direct band gap, and the sensitivity of the transition metal chalcogenide is higher.
At present, among the methods for preparing a two-dimensional transition metal chalcogenide, the main methods are: lift-off methods and chemical vapor deposition methods.
The stripping method is a traditional method for preparing two-dimensional transition metal sulfide, and mainly comprises the following steps: ion intercalation stripping and mechanical stripping. For example, chinese patent CN108423642a discloses a method for preparing a small-size transition metal chalcogenide two-dimensional nanosheet, which takes bulk powder of a transition metal chalcogenide as a raw material and a polymer as an auxiliary agent, and prepares the transition metal chalcogenide two-dimensional nanosheet with different sizes and different components by polymer-assisted ball milling, including 3 steps: weighing block powder prepared by high polymer and high polymer-assisted ball milling; ball milling and stripping, adding water, mixing and taking out; and (5) performing gradient centrifugation to obtain products with different sizes, and purifying to remove redundant macromolecules. The method has simple process, but cannot prepare large-area continuous two-dimensional transition metal chalcogenide, and the two-dimensional transition metal chalcogenide obtained by the stripping method is relatively dispersed, so that the method cannot meet the requirements of industrial and commercial production.
In addition to the conventional stripping method, a more emerging chemical vapor deposition method is concerned by more and more researchers, for example, chinese patent CN110155959a discloses a limited-area chemical vapor deposition preparation method of a two-dimensional transition metal alloy chalcogenide. The method for preparing the two-dimensional transition metal chalcogenide has poor stability, and the randomness of nucleation of the two-dimensional transition metal chalcogenide on the substrate is high, so how to make the nucleation of the two-dimensional transition metal chalcogenide on the substrate more stable, and the obtaining of the large-area, continuous and high-quality two-dimensional transition metal chalcogenide film becomes a key problem to be solved urgently for preparing flexible electrons.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and a device of a large-area continuous two-dimensional transition metal sulfur compound film, and aims to solve the problems that the stability of the existing chemical vapor deposition method is poor, and the randomness of nucleation of a two-dimensional transition metal sulfur group compound on a substrate is high.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the invention relates to an open quartz boat, wherein one end of the open quartz boat is provided with an opening, when chemical vapor deposition is carried out, the two open quartz boats are used as carriers, and the open ends of the two open quartz boats are opposite to each other, so that turbulent flow is prevented from being formed at the opposite ends of the open quartz boats, and the airflow is more stable.
Preferably, the height of the open quartz boat is 1.5cm, the width is 2.5cm, the length is 10cm, and the thickness is 0.2cm.
The invention also relates to a preparation method of the large-area continuous two-dimensional transition metal sulfur compound film based on the open quartz boat, which comprises the following steps:
1) Preparing a chemical vapor deposition precursor: weighing precursor powder, and placing the precursor powder in an open quartz boat A, wherein the precursor powder is placed at one end of the open quartz boat A, which is provided with an opening;
2) Preparing a sulfur source or a selenium source by chemical vapor deposition: weighing a sulfur source or a selenium source, and placing the sulfur source or the selenium source in an open quartz boat B;
3) Preparing a catalyst: dissolving a catalyst in deionized water to form a catalyst solution, soaking a substrate in the catalyst solution, drying the substrate by inert gas after soaking, and inversely covering the substrate above precursor powder in the open quartz boat A;
4) The opening quartz boat A is loaded by a quartz plate base and then is placed in a main furnace heating area of the tube furnace, the opening quartz boat B is integrally placed in a preheating heating area of the tube furnace, the main furnace heating area is communicated with the preheating heating area, one opening end of the opening quartz boat A is opposite to one opening end of the opening quartz boat B, turbulence is prevented from being formed at the opposite ends of the opening quartz boat A and the opening quartz boat B, and therefore airflow is more stable;
5) Setting the heating temperature and the maintaining time of a main furnace heating area and a preheating heating area, heating the precursor to form precursor steam by the main furnace heating area, and starting heating a sulfur source or a selenium source by the preheating heating area to form sulfur source steam or selenium source steam after the main furnace heating area is heated to the set temperature;
6) And reacting the precursor vapor with sulfur source vapor or reacting the precursor vapor with selenium source vapor to generate a two-dimensional transition metal chalcogenide and depositing the two-dimensional transition metal chalcogenide on the surface of the substrate to form the two-dimensional transition metal chalcogenide film.
Preferably, the precursor is tungsten trioxide or molybdenum trioxide; the sulfur source is S powder, and the selenium source is Se powder; the two-dimensional transition metal chalcogenide film is WS 2 Or MoS 2 Or WSe 2 Or MoSe 2 A film.
Preferably, the mass of the tungsten trioxide and the molybdenum trioxide is controlled to be between 70 and 80 mg.
Preferably, the quality of the sulfur source or the selenium source is controlled between 180 and 200 mg.
Preferably, the catalyst is NaCl, when preparing NaCl solution, 20-25 mgNaCl crystals are put into a beaker and dissolved in 100-125 ml of deionized water, and the deionized water is stirred by a glass rod to accelerate the dissolution of the NaCl crystals; the purity of the NaCl crystal is higher than 99.9%.
Preferably, before heating the precursor in step 5), the tube furnace is evacuated, and then inert gas is introduced, wherein the inert gas is always introduced into the tube furnace during the processes of heating the precursor, heating the sulfur source or the selenium source, and generating the two-dimensional transition metal chalcogenide.
Preferably, the inert gas adopts argon, and the argon is introduced into the tubular furnace at the flow rate of 100-200 sccm.
Preferably, the heating temperature of the main furnace heating zone set in the step 5) is 950-1000 ℃, and the maintaining time of the main furnace heating zone is 30-40 min; the heating temperature of the preheating zone is set to be 120-150 ℃, and the maintaining time of the preheating zone is 40-50 min.
The width of the quartz plate base is 3-4 cm, the length of the quartz plate base is 10cm, and the thickness of the quartz plate base is 0.2cm.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. when the two-dimensional transition metal sulfur compound film is generated by chemical vapor deposition, precursor powder is placed in an open quartz boat A with an opening at one end, a sulfur source or a selenium source is placed in an open quartz boat B with an opening at one end, when the open quartz boat A and the open quartz boat B are placed in a tube furnace, the open ends of the open quartz boat A and the open end of the open quartz boat B are opposite, and the chemical vapor deposition is carried out under the arrangement, so that turbulence can be prevented from being formed at the front part of the open quartz boat to a great extent, nucleation points of the two-dimensional transition metal sulfur compound on a substrate are more stable, and the problem that the randomness of the two-dimensional transition metal sulfur compound is large when the conventional open quartz boat is used for growing the two-dimensional transition metal sulfur compound is solved.
2. The invention only needs one precursor, and does not need to grow in the process of growthH 2 The method promotes the large-area continuous growth of the film material, can obtain the large-area continuous film material only in the inert gas environment, and has the characteristics of low cost, simple device, easy operation, good controllability and the like.
Drawings
FIG. 1 is a conventional closed-port quartz boat;
FIG. 2 is a schematic view of the structure of an open quartz boat for use in the present invention;
FIG. 3 is a diagram showing an apparatus for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to the present invention;
FIG. 4 is a schematic diagram of a quartz wafer pedestal;
FIG. 5 is a flow chart of the preparation of a large area continuous two-dimensional transition metal sulfur compound thin film;
FIG. 6 is a schematic view of the precursor being tiled on an open quartz boat A;
FIG. 7 is a schematic view of a sulfur source (or selenium source) laid flat in an open quartz boat B;
FIG. 8 is a schematic view of the substrates being flipped over on the open quartz boat A;
FIG. 9 shows WS prepared in example 2 of the present invention 2 Optical microscopy of thin films;
Detailed Description
For further understanding of the present invention, the present invention will be described in detail with reference to examples, which are provided for illustration of the present invention but are not intended to limit the scope of the present invention.
Example one
Referring to fig. 2, one end of the open-ended quartz boat according to this embodiment is provided with an opening, and when performing chemical vapor deposition, the two open-ended quartz boats are used as carriers, and the open ends of the two open-ended quartz boats are opposite to each other, so that turbulence at the opposite ends of the open-ended quartz boats can be avoided, and the gas flow is more stable. The height of the open quartz boat is 1.5cm, the width is 2.5cm, the length is 10cm, and the thickness is 0.2cm.
Example two
Referring to fig. 3, the embodiment further relates to a device for preparing a large-area continuous two-dimensional transition metal sulfur compound film, which includes a tube furnace, an open quartz boat a1002 for containing a precursor and a substrate adsorbed with a catalyst, and an open quartz boat B1003 for containing a sulfur source or a selenium source, wherein the open quartz boat a and the open quartz boat B are both the open quartz boats according to embodiment 1. The tube furnace comprises a main furnace heating zone 1007 and a preheating heating zone 1008, and the main furnace heating zone 1007 and the preheating heating zone 1008 are communicated with each other.
The open quartz boat a1002 and the open quartz boat B1003 used in the present invention have openings at their ends, as compared to the conventional closed open quartz boat shown in fig. 1. The bottom of the open quartz boat A1002 is provided with a quartz plate base 1009 shown in FIG. 4, the open quartz boat A1002 is placed in the main furnace heating zone 1007, the open quartz boat B1003 is placed in the center of the preheating heating zone, and the ends of the open quartz boat A1002 and the open quartz boat B1003 provided with openings are opposite.
The height of the open quartz boat A1002 and the height of the open quartz boat B1003 are both 1.5cm, the width is 2.5cm, the length is 10cm, and the thickness is 0.2cm; the quartz piece base 1009 has a width of 3 to 4cm, a length of 10cm, and a thickness of 0.2cm.
EXAMPLE III
This example relates to a method for preparing large-area continuous two-dimensional transition metal sulfur compound film, before preparation, two open quartz boats as shown in fig. 2 are prepared, respectively marked as open quartz boat a1002 and open quartz boat B1003, and the structures of the open quartz boat a1002 and the open quartz boat B1003 are as described in the first example. Cleaning the open quartz boat A1002 and the open quartz boat B1003 by using clean water, putting the cleaned open quartz boat A1002 and the open quartz boat B1003 into an ultrasonic machine for ultrasonic treatment for 10min, further cleaning the open quartz boat A1002 and the open quartz boat B1003, and after cleaning is finished, putting the open quartz boat A1002 and the open quartz boat B1003 into a drying box for drying and standby.
Referring to fig. 5, the preparation of the large-area continuous two-dimensional transition metal sulfur compound thin film comprises the following steps:
1) Preparing a chemical vapor deposition precursor: referring to FIG. 6, 70mg of WO was weighed 3 The powder is used as precursor powder 1004 and is placed in an open quartz boat A1002 with an opening at one end, and the precursor isPlacing the powder 1004 at one end of the quartz boat A with the opening, wherein the precursor powder 1004 is tiled in an interval of 0.8 cm-1 cm in length and about 0.5cm in width;
2) Preparing a sulfur source or a selenium source by chemical vapor deposition: weighing a sulfur source or a selenium source 1005, wherein the sulfur source is adopted in the embodiment, specifically, S powder is adopted, 200mg of the S powder is weighed as shown in the attached drawing 7, and the S powder is uniformly spread in the whole quartz boat B1003 with an opening;
3) Preparing a catalyst: dissolving a catalyst (NaCl crystals with purity higher than 99.9%) in 100ml of deionized water, stirring the deionized water by using a glass rod, accelerating the dissolution of the NaCl crystals to form a catalyst solution, soaking the substrate 1006 in the catalyst solution, wherein the substrate 1006 in the embodiment is made of sapphire for 5 minutes, drying moisture on the surface of the substrate 1006 by using inert gas (argon) after the substrate 1006 is soaked, and reversely buckling the substrate 1006 in the open quartz boat A1002 and above the precursor powder 1004;
4) The method comprises the following steps of carrying an open quartz boat A1002 by a quartz plate base 1009, then placing the quartz boat A1003 at the central position of a main furnace heating area 1007 of the tube furnace, placing the open quartz boat B1003 in the central position of a preheating heating area 1008 of the tube furnace, wherein the main furnace heating area 1007 is communicated with the preheating heating area 1008, and the open quartz boat A1002 is opposite to the open end of the open quartz boat B1003;
5) Setting the heating temperature and the maintaining time of the heating zone 1007 and the preheating zone 1008 of the main furnace, wherein in the embodiment, the heating temperature of the heating zone 1007 of the main furnace is 975 ℃ and the time is 30min; setting the heating temperature of the preheating zone 1008 to 150 ℃ for 40min; before heating the precursor, the tube furnace is vacuumized, inert gas (argon) is introduced, and the heating zone 1007 of the main furnace is used for heating the precursor powder (WO) 3 Powder) 1004, heating to 975 ℃ after 1 hour, maintaining for 30min, then naturally cooling the main furnace heating zone 1007, and forming precursor steam in the main furnace heating zone 1007; and when the heating zone 1007 of the main furnace is heated to the set temperature (975 ℃), the preheating heating zone 1008 starts to heat the S powder 1005, the temperature is raised to 150 ℃ after 10min, the temperature is maintained for 40min, and then the preheating heating zone 1008 is naturally cooled to form the powderSulfur source steam; argon gas was introduced into the tube furnace at a flow rate of 150sccm throughout the process.
6) The precursor vapor and the sulfur source vapor react to form a two-dimensional transition metal chalcogenide and deposit on the surface of the substrate 1006 to form a two-dimensional transition metal chalcogenide thin film (WS) as shown in FIG. 9 2 A film).
Example four
This example relates to a method for preparing large-area continuous two-dimensional transition metal sulfur compound film, before preparation, two open quartz boats as shown in fig. 2 are prepared, respectively marked as open quartz boat a1002 and open quartz boat B1003, and the structures of the open quartz boat a1002 and the open quartz boat B1003 are as described in the first example. Cleaning the open quartz boat A1002 and the open quartz boat B1003 by using clean water, putting the cleaned open quartz boat A1002 and the open quartz boat B1003 into an ultrasonic machine for ultrasonic treatment for 10min, further cleaning the open quartz boat A1002 and the open quartz boat B1003, and after cleaning is finished, putting the open quartz boat A1002 and the open quartz boat B1003 into a drying box for drying and standby.
Referring to fig. 5, the preparation of the large-area continuous two-dimensional transition metal sulfur compound thin film comprises the following steps:
1) Preparing a chemical vapor deposition precursor: referring to FIG. 6, 70mg of WO was weighed 3 The powder was placed as precursor powder 1004 in an open quartz boat A1002 having an opening at one end, and the precursor powder 1004 was placed (WO powder 1004) 3 Powder) to the end of the open quartz boat a where the opening is provided, precursor powder 1004 (WO) 3 Powder) is spread in a range of 0.8cm to 1cm in length and about 0.5cm in width;
2) Preparing a sulfur source or a selenium source by chemical vapor deposition: weighing a sulfur source or a selenium source 1005, wherein the selenium source is adopted in the embodiment, specifically, se powder is adopted, and 200mg of Se powder is weighed and uniformly spread in the whole quartz boat B1003 with an opening, as shown in the attached figure 7;
3) Preparing a catalyst: dissolving a catalyst (NaCl crystals with purity higher than 99.9%) in 100ml of deionized water, stirring the deionized water with a glass rod to accelerate the dissolution of the NaCl crystals to form a catalyst solution, and soaking a substrate 1006 with the catalyst solution, wherein the substrate 1006 in this embodiment uses a substrate with a solution of the catalystThe soaking time of sapphire is 5 minutes, after the substrate 1006 is soaked, the moisture on the surface of the substrate 1006 is blown dry by inert gas (argon), the substrate 1006 is reversely buckled in the open quartz boat A1002 and is positioned in the precursor powder 1004 (WO) 3 Powder) above;
4) The method comprises the following steps of carrying an open quartz boat A1002 by a quartz plate base 1009, then placing the quartz boat A1003 at the central position of a main furnace heating area 1007 of the tube furnace, placing the open quartz boat B1003 in the central position of a preheating heating area 1008 of the tube furnace, wherein the main furnace heating area 1007 is communicated with the preheating heating area 1008, and the open quartz boat A1002 is opposite to the open end of the open quartz boat B1003;
5) Setting the heating temperature and the maintaining time of the heating zone 1007 and the preheating zone 1008 of the main furnace, wherein in the embodiment, the heating temperature of the heating zone 1007 of the main furnace is 975 ℃ and the time is 30min; setting the heating temperature of the preheating zone 1008 to 150 ℃ for 40min; before heating the precursor, the tube furnace is evacuated, then inert gas (argon) is introduced, and the heating zone 1007 of the main furnace first heats the precursor powder (WO) 3 Powder) 1004, heating to 975 ℃ for 30min after 1 hour, then naturally cooling a main furnace heating zone 1007, and forming precursor vapor in the main furnace heating zone 1007; and when the heating zone 1007 of the main furnace is heated to the set temperature (975 ℃), the preheating heating zone 1008 starts to heat the Se powder 1005, the temperature is raised to 150 ℃ after 10min, the temperature is maintained for 40min, and then the preheating heating zone 1008 is naturally cooled to form selenium source steam; argon gas was introduced into the tube furnace at a flow rate of 150sccm throughout the process.
6) The precursor vapor reacts with the selenium source vapor to generate a two-dimensional transition metal chalcogenide which is deposited on the surface of the substrate 1006 to form a two-dimensional transition metal chalcogenide film (WSe) 2 A film).
EXAMPLE five
This example relates to a method for preparing large-area continuous two-dimensional transition metal sulfur compound film, before preparation, two open quartz boats as shown in fig. 2 are prepared, respectively marked as open quartz boat a1002 and open quartz boat B1003, and the structures of the open quartz boat a1002 and the open quartz boat B1003 are as described in the first example. Cleaning the open quartz boat A1002 and the open quartz boat B1003 by using clear water, placing the quartz boat A1002 and the open quartz boat B1003 in an ultrasonic machine for 10min by ultrasonic treatment, further cleaning the open quartz boat A1002 and the open quartz boat B1003, and after cleaning is finished, placing the open quartz boat A1002 and the open quartz boat B1003 in a drying box for drying and standby.
Referring to fig. 5, the preparation of the large-area continuous two-dimensional transition metal sulfur compound thin film is as follows:
1) Preparing a chemical vapor deposition precursor: referring to FIG. 6, 70mg of MoO was weighed 3 The powder was placed as precursor powder 1004 in an open quartz boat A1002 having an opening at one end, and the precursor powder 1004 (MoO) 3 Powder) to the open-ended quartz boat a, precursor powder 1004 (MoO) was placed on the open-ended quartz boat a 3 Powder) is spread in a range of 0.8cm to 1cm in length and about 0.5cm in width;
2) Preparing a sulfur source or a selenium source by chemical vapor deposition: weighing a sulfur source or a selenium source 1005, wherein the sulfur source is adopted in the embodiment, specifically, S powder is adopted, 200mg of the S powder is weighed as shown in the attached figure 7, and the S powder is uniformly spread in the whole quartz boat B1003 with an opening;
3) Preparing a catalyst: dissolving a catalyst (NaCl crystals with purity higher than 99.9%) in 100ml of deionized water, stirring the deionized water with a glass rod to accelerate the dissolution of the NaCl crystals to form a catalyst solution, soaking the substrate 1006 with the catalyst solution, wherein the substrate 1006 is made of sapphire in the embodiment, the soaking time is 5 minutes, after the substrate 1006 is soaked, blowing moisture on the surface of the substrate 1006 with inert gas (argon), and inversely buckling the substrate 1006 in an open quartz boat A1002 and locating in precursor powder 1004 (MoO) 3 Powder) above;
4) The method comprises the following steps of carrying an open quartz boat A1002 by a quartz plate base 1009, then placing the quartz boat A1003 at the central position of a main furnace heating area 1007 of the tube furnace, placing the open quartz boat B1003 in the central position of a preheating heating area 1008 of the tube furnace, wherein the main furnace heating area 1007 is communicated with the preheating heating area 1008, and the open quartz boat A1002 is opposite to the open end of the open quartz boat B1003;
5) The heating temperatures of the main furnace heating zone 1007 and the preheating heating zone 1008 are set to be equal toMaintaining time, in this embodiment, the heating temperature of the heating zone 1007 of the main furnace is set to 975 ℃, and the time is set to 30min; setting the heating temperature of the preheating zone 1008 to 150 ℃ for 40min; before heating the precursor, the tube furnace is vacuumized, inert gas (argon) is introduced, and the heating zone 1007 of the main furnace is used for heating the precursor powder (MoO) 3 Powder) 1004, heating to 975 ℃ after 1 hour, maintaining for 30min, then naturally cooling the main furnace heating zone 1007, and forming precursor steam in the main furnace heating zone 1007; when the temperature of the heating zone 1007 of the main furnace rises to the set temperature (975 ℃), the preheating heating zone 1008 starts to heat the S powder 1005, the temperature rises to 150 ℃ after 10min, the temperature is maintained for 40min, and then the preheating heating zone 1008 is naturally cooled to form sulfur source steam; argon gas was introduced into the tube furnace at a flow rate of 150sccm throughout the process.
6) The precursor vapor reacts with the sulfur source vapor to generate a two-dimensional transition metal chalcogenide which is deposited on the surface of the substrate 1006 to form a two-dimensional transition metal chalcogenide thin film (WoS) 2 A film).
Example six
This example relates to a method for preparing large-area continuous two-dimensional transition metal sulfur compound film, before preparation, two open quartz boats as shown in fig. 2 are prepared, respectively marked as open quartz boat a1002 and open quartz boat B1003, and the structures of the open quartz boat a1002 and the open quartz boat B1003 are as described in the first example. Cleaning the open quartz boat A1002 and the open quartz boat B1003 by using clean water, putting the cleaned open quartz boat A1002 and the open quartz boat B1003 into an ultrasonic machine for ultrasonic treatment for 10min, further cleaning the open quartz boat A1002 and the open quartz boat B1003, and after cleaning is finished, putting the open quartz boat A1002 and the open quartz boat B1003 into a drying box for drying and standby.
Referring to fig. 5, the preparation of the large-area continuous two-dimensional transition metal sulfur compound thin film comprises the following steps:
1) Preparing a chemical vapor deposition precursor: referring to FIG. 6, 70mg of MoO was weighed 3 The powder was placed as precursor powder 1004 in an open quartz boat A1002 having an opening at one end, and the precursor powder 1004 (MoO) 3 Powder) is arranged at one end of the open quartz boat A, which is provided with an opening, and precursor powder is arrangedPowder 1004 (MoO) 3 Powder) is spread in a range of 0.8cm to 1cm in length and about 0.5cm in width;
2) Preparing a sulfur source or a selenium source by chemical vapor deposition: weighing a sulfur source or a selenium source 1005, wherein the selenium source is adopted in the embodiment, specifically, se powder is adopted, and 200mg of Se powder is weighed and uniformly spread in the whole quartz boat B1003 with an opening, as shown in the attached figure 7;
3) Preparing a catalyst: dissolving a catalyst (NaCl crystals with purity higher than 99.9%) in 100ml of deionized water, stirring the deionized water with a glass rod to accelerate the dissolution of the NaCl crystals to form a catalyst solution, soaking the substrate 1006 with the catalyst solution, wherein the substrate 1006 is made of sapphire in the embodiment, the soaking time is 5 minutes, after the substrate 1006 is soaked, blowing moisture on the surface of the substrate 1006 with inert gas (argon), and reversely buckling the substrate 1006 in the open quartz boat A1002 and locating in precursor powder 1004 (MoO) 3 Powder) above;
4) The method comprises the following steps of carrying an open quartz boat A1002 by a quartz plate base 1009, then placing the quartz boat A1003 at the central position of a main furnace heating area 1007 of the tube furnace, placing the open quartz boat B1003 in the central position of a preheating heating area 1008 of the tube furnace, wherein the main furnace heating area 1007 is communicated with the preheating heating area 1008, and the open quartz boat A1002 is opposite to the open end of the open quartz boat B1003;
5) Setting the heating temperature and the maintaining time of the heating zone 1007 and the preheating zone 1008 of the main furnace, wherein in the embodiment, the heating temperature of the heating zone 1007 of the main furnace is 975 ℃ and the time is 30min; setting the heating temperature of the preheating zone 1008 to 150 ℃ for 40min; before heating the precursor, the tube furnace is evacuated, then inert gas (argon) is introduced, and the heating zone 1007 of the main furnace first heats the precursor powder (MoO) 3 Powder) 1004, heating to 975 ℃ for 30min after 1 hour, then naturally cooling a main furnace heating zone 1007, and forming precursor vapor in the main furnace heating zone 1007; and when the heating zone 1007 of the main furnace is heated to the set temperature (975 ℃), the preheating heating zone 1008 starts to heat the Se powder 1005, the temperature is raised to 150 ℃ after 10min, the temperature is maintained for 40min, and then the preheating heating zone 1008 is naturally cooled to form selenium source steam; in-planeIn the process, argon gas was introduced into the tube furnace at a flow rate of 150sccm all the time.
6) The precursor vapor reacts with the selenium source vapor to generate a two-dimensional transition metal chalcogenide which is deposited on the surface of the substrate 1006 to form a two-dimensional transition metal chalcogenide film (WoSe) 2 A film).
The present invention has been described in detail with reference to the embodiments, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.

Claims (9)

1. A preparation method of a large-area continuous two-dimensional transition metal sulfur compound film is characterized by comprising the following steps: which comprises the following steps:
1) Preparing a chemical vapor deposition precursor: weighing precursor powder, placing the precursor powder in an open quartz boat A, and placing the precursor powder at one end of the open quartz boat A, which is provided with an opening;
2) Preparing a sulfur source or a selenium source by chemical vapor deposition: weighing a sulfur source or a selenium source, and placing the sulfur source or the selenium source in an open quartz boat B;
3) Preparing a catalyst: dissolving a catalyst in deionized water to form a catalyst solution, soaking a substrate in the catalyst solution, drying the substrate by inert gas after soaking, and inversely covering the substrate above precursor powder in the open quartz boat A;
4) The opening quartz boat A is loaded by a quartz plate base and then is placed in a main furnace heating area of the tube furnace, the opening quartz boat B is integrally placed in a preheating heating area of the tube furnace, the main furnace heating area is communicated with the preheating heating area, one opening end of the opening quartz boat A is opposite to one opening end of the opening quartz boat B, turbulence is prevented from being formed at the opposite ends of the opening quartz boat A and the opening quartz boat B, and therefore airflow is more stable;
5) Setting the heating temperature and the maintaining time of a main furnace heating area and a preheating heating area, heating the precursor to form precursor steam by the main furnace heating area, and starting heating a sulfur source or a selenium source by the preheating heating area to form sulfur source steam or selenium source steam after the main furnace heating area is heated to the set temperature;
6) And reacting the precursor vapor with sulfur source vapor or reacting the precursor vapor with selenium source vapor to generate a two-dimensional transition metal chalcogenide and depositing the two-dimensional transition metal chalcogenide on the surface of the substrate to form the two-dimensional transition metal chalcogenide film.
2. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 1, characterized in that: the height of the open quartz boat is 1.5cm, the width is 2.5cm, the length is 10cm, and the thickness is 0.2cm.
3. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 1, characterized in that: the precursor is tungsten trioxide or molybdenum trioxide; the sulfur source is S powder, and the selenium source is Se powder; the two-dimensional transition metal chalcogenide film is WS 2 Or MoS 2 Or WSe 2 Or MoSe 2 A film.
4. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 3, characterized in that: the mass of the tungsten trioxide and the molybdenum trioxide is controlled to be 70 to 80mg.
5. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 3, characterized in that: the quality of the sulfur source or the selenium source is controlled to be 180 to 200mg.
6. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 1, characterized in that: the catalyst is NaCl, when a NaCl solution is prepared, 20 to 25mgNaCl crystals are placed in a beaker and dissolved in 100 to 125ml of deionized water, and the deionized water is stirred by a glass rod to accelerate the dissolution of the NaCl crystals; the purity of the NaCl crystal is higher than 99.9%.
7. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 1, characterized in that: before heating the precursor in the step 5), vacuumizing the tube furnace, then introducing inert gas, and introducing the inert gas into the tube furnace all the time in the processes of heating the precursor, heating the sulfur source or the selenium source and generating the two-dimensional transition metal chalcogenide.
8. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 7, characterized in that: the inert gas adopts argon and is introduced into the tubular furnace at the flow rate of 100 to 200sccm.
9. The method for producing a large-area continuous two-dimensional transition metal sulfur compound thin film according to claim 1, characterized in that: the heating temperature of the main furnace heating zone set in the step 5) is 950 to 1000 ℃, and the maintaining time of the main furnace heating zone is 30 to 40min; the heating temperature of the preheating heating zone is set to be 120-150 ℃, and the maintaining time of the preheating heating zone is 40-50min.
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