CN115354392B - Preparation method of large-size monocrystalline molybdenum disulfide - Google Patents
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- CN115354392B CN115354392B CN202210982776.2A CN202210982776A CN115354392B CN 115354392 B CN115354392 B CN 115354392B CN 202210982776 A CN202210982776 A CN 202210982776A CN 115354392 B CN115354392 B CN 115354392B
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Abstract
The application relates to a preparation method of large-size monocrystalline molybdenum disulfide, which comprises the following steps: placing a sulfur source in a first temperature zone, placing a molybdenum source and ferrous chloride powder in a second temperature zone, and placing a sapphire substrate in a third temperature zone; passing a carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone in sequence; and heating the first temperature zone, the second temperature zone and the third temperature zone to respective preset temperatures to grow single-crystal molybdenum disulfide. According to the preparation method, a ferrous chloride assisted chemical vapor deposition method is adopted, a wafer-level single crystal molybdenum disulfide film can be prepared on a common non-chamfer sapphire substrate, the energy band structure of molybdenum disulfide can be further regulated and controlled by iron doping, and the contact between a channel and an electrode is optimized; the method is simple and easy to operate, the process is controllable, and the obtained molybdenum disulfide crystal domains are consistent in orientation and have no domain grain boundaries, so that good layer number uniformity and crystal quality are shown.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a preparation method of large-size monocrystalline molybdenum disulfide.
Background
With the continuous downsizing and increasing integration of silicon-based transistors, short channel effect and thermal effect are more and more remarkable, and the operation speed and performance of the existing electronic device are close to the limit of silicon-based materials, so that the development of novel semiconductor materials and devices is particularly critical. The atomic layer thickness and the excellent static control capability of the novel two-dimensional semiconductor material represented by single-layer molybdenum disulfide can effectively reduce the working voltage/current and energy consumption; the lack of dangling bonds on the surface can reduce the reduction of carrier mobility caused by scattering; the rich energy band structure facilitates the design of a variety of new logic and memory devices. Therefore, it is considered as a core candidate for the next-generation revolutionary technology application satisfying various demands.
The development of high-performance field effect transistors, integrated circuits and high-end general purpose chips is necessarily based on high-quality, large-area, uniform-layer-number large-size two-dimensional single crystal materials. The main reasons are as follows: (1) The monocrystalline material effectively avoids the formation of grain boundaries in the polycrystalline material, so that the intrinsic performance of the material is extremely exerted; (2) The two-dimensional monocrystal is used as a primitive material, so that uniformity and stability of device performance can be ensured; (3) Large-sized single crystal domains are critical to ensure stable electrical performance and high device yields. However, since two-dimensional materials have lower dimensions, conventional three-dimensional single crystal growth techniques cannot be directly applied to the synthesis of two-dimensional materials. The new material preparation technology is developed to realize the synthesis of the wafer-size two-dimensional semiconductor single crystal, and the technology becomes the most core scientific and technical problem in the field of low-dimensional nano materials.
Due to the differences in symmetry and domain edge termination types, as well as the differences in growth substrates, existing two-dimensional single crystal preparation techniques are difficult to directly extend to large-scale growth on a two-dimensional semiconductor wafer scale. In the related art, a step regulation mechanism of a specially-made sapphire substrate is utilized to realize the controllable preparation of two-inch single-crystal molybdenum disulfide and tungsten disulfide, and although the size is improved, the requirement of a high-performance device on the size of two-dimensional single-crystal molybdenum disulfide still cannot be met. In addition, the growth substrate selected by the preparation method is specially made of sapphire, and special processing treatment is needed for the sapphire substrate in order to introduce parallel steps on the surface of the sapphire, so that the surface of the sapphire has a chamfer angle within 0.5 degrees relative to the crystal axis of the sapphire, and the sapphire processing and material preparation cost is greatly increased due to the high-precision chamfer angle. In addition, the sapphire substrate needs to be subjected to high-temperature pre-annealing treatment for a long time at the temperature of more than 1000 ℃ before the two-dimensional semiconductor material grows, so that the material preparation process is more complicated.
It can be seen that the development of a mild, low cost, controllable preparation of high quality wafer size two-dimensional molybdenum disulfide single crystals is critical for high performance electronics and integrated circuit applications.
Disclosure of Invention
The embodiment of the application provides a preparation method of large-size monocrystalline molybdenum disulfide, which aims to solve the problem that the distribution size of a monocrystalline molybdenum disulfide film is small in the related art.
The application provides a preparation method of large-size monocrystalline molybdenum disulfide, which comprises the following steps:
placing a sulfur source in a first temperature zone, placing a molybdenum source and ferrous chloride powder in a second temperature zone, and placing a sapphire substrate in a third temperature zone;
passing a carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone in sequence;
and heating the first temperature zone, the second temperature zone and the third temperature zone to respective preset temperatures to grow single-crystal molybdenum disulfide.
In some embodiments, the mass ratio between the sulfur source, the molybdenum source, and the ferric chloride powder is (200-230): (8-10): (1-3).
In some embodiments, the predetermined temperature of the first temperature zone is 190-230 ℃, the predetermined temperature of the second temperature zone is 900-910 ℃, and the predetermined temperature of the third temperature zone is 900-910 ℃.
In some embodiments, the distance between the sulfur source and the molybdenum source is 8-10 cm;
and/or the distance between the molybdenum source and the sapphire substrate is 1-3 cm.
In some embodiments, the sulfur source comprises sulfur powder;
and/or the molybdenum source comprises molybdenum trioxide powder.
In some embodiments, the single crystal molybdenum disulfide is grown for a period of 5 to 60 minutes.
In some embodiments, the carrier gas has a flow rate of 60 to 80sccm.
In some embodiments, the placing of the sapphire substrate is preceded by:
and removing impurities on the surface of the sapphire substrate.
In some embodiments, prior to passing the carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone, the method of preparing further comprises:
and vacuumizing the first temperature zone, the second temperature zone and the third temperature zone to below 5 Pa.
In some embodiments, after the growth of the single crystal molybdenum disulfide is finished, stopping introducing the carrier gas, and cooling the first temperature region, the second temperature region and the third temperature region to room temperature to obtain the large-size single crystal molybdenum disulfide.
The technical scheme provided by the application has the beneficial effects that: 1) By adopting a ferrous chloride-assisted chemical vapor deposition method, a wafer-level single crystal molybdenum disulfide film with the distribution size of 4 inches can be prepared on a common non-chamfer sapphire substrate, the energy band structure of molybdenum disulfide can be further regulated and controlled by iron doping, and the contact between a channel and an electrode is optimized, so that the preparation of a high-performance electronic device is facilitated;
2) The method is simple and easy to operate, the process is controllable, and the obtained molybdenum disulfide crystal domains have consistent orientation and no domain grain boundary, and show good layer number uniformity and crystal quality.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an optical microscopic image of a molybdenum disulfide film provided in example 1 of the present application;
FIG. 2 is an optical microscopic image of a molybdenum disulfide film provided in example 2 of the present application;
FIG. 3 is an optical microscopic image of a molybdenum disulfide film provided in example 3 of the present application;
FIG. 4 is an optical microscopic image of a molybdenum disulfide film provided in example 4 of the present application;
FIG. 5 is an optical microscopic image of a molybdenum disulfide film provided in example 5 of the present application;
FIG. 6 is an atomic force microscope image of a molybdenum disulfide film provided in example 1 of the present application;
FIG. 7 is a Raman spectrum of the molybdenum disulfide film provided in example 1 of the present application;
FIG. 8 is a transmission electron micrograph of a molybdenum disulfide film provided in an embodiment of the present application;
FIG. 9 is an electron diffraction pattern of a molybdenum disulfide film provided in an embodiment of the present application;
FIG. 10 is a double-spherical aberration correcting scanning transmission electron micrograph of a molybdenum disulfide film provided in an embodiment of the present application;
FIG. 11 is a low energy electron diffraction pattern of a molybdenum disulfide film provided by an embodiment of the present application;
FIG. 12 is a graph showing the optical microscopic comparison of a molybdenum disulfide sample provided in the embodiment of the present application before and after oxygen etching;
FIGS. 13 (a) - (b) are graphs showing performance characteristics of an electronic device when the molybdenum disulfide film provided in the embodiment of the present application is applied to a silicon dioxide/silicon substrate, wherein FIG. 13 (a) is a transfer characteristic graph, and FIG. 13 (b) is an output characteristic graph at different gate voltages;
FIGS. 14 (a) - (b) are graphs showing the performance characterization of the electronic device of the field effect transistor by applying the samples of the molybdenum disulfide film provided in example 1 to the field effect transistor, wherein FIG. 14 (a) is a graph showing the transfer characteristics of the transistor prepared by the molybdenum disulfide film at different positions, and FIG. 14 (b) is a graph showing the current switching ratio and mobility of the transistor prepared by the molybdenum disulfide film at different positions;
FIG. 15 is an optical microscopic image of a molybdenum disulfide film provided in comparative example 1 of the present application;
FIG. 16 is an optical microscopic image of a molybdenum disulfide film provided in comparative example 2 of the present application;
FIG. 17 is an optical microscopic image of a molybdenum disulfide film provided in comparative example 3 of the present application;
FIG. 18 is an optical microscopic image of a molybdenum disulfide film provided in comparative example 4 of the present application;
FIG. 19 is an optical microscopic image of a molybdenum disulfide film provided in comparative example 5 of the present application;
FIG. 20 is an optical micrograph of a molybdenum disulfide film provided in comparative example 6 of the present application;
fig. 21 is an optical microscopic image of a molybdenum disulfide film provided in comparative example 7 of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The embodiment of the application provides a preparation method of large-size monocrystalline molybdenum disulfide, which comprises the following steps:
placing a sulfur source in a first temperature zone, placing a molybdenum source and ferrous chloride powder in a second temperature zone, and placing a sapphire substrate in a third temperature zone;
passing a carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone in sequence;
and heating the first temperature zone, the second temperature zone and the third temperature zone to respective preset temperatures to grow single-crystal molybdenum disulfide.
The preparation method can adopt a three-temperature-zone tube furnace vapor deposition system with independent temperature control, the three-section temperature zone can have different heating temperatures to meet the reaction requirement, wherein a sulfur source is positioned in an upstream first temperature zone, the sulfur source enters a third temperature zone along with carrier gas after heating and volatilizing, and meanwhile, a molybdenum source and ferrous chloride positioned in the middle stream enter the third temperature zone along with the carrier gas after heating and volatilizing, so that the problems of overhigh nucleation density and uncontrollable layer number caused by incapability of independent control of the evaporation temperature and the growth temperature of the molybdenum source in the traditional chemical vapor deposition process are avoided, the third temperature zone is a main reaction zone, the upstream sulfur, molybdenum and iron vapor are conveyed to the surface of a sapphire substrate to start pre-nucleate, the sulfur source reacts with the molybdenum source to generate molybdenum disulfide, and after ferrous chloride is decomposed, the iron element replaces a molybdenum atom site in the molybdenum disulfide to form an iron-doped large-area two-dimensional single crystal molybdenum disulfide product.
Specifically, the first temperature zone, the second temperature zone, and the third temperature zone are sequentially arranged in the horizontal direction.
In some embodiments, the mass ratio between the sulfur source, the molybdenum source, and the ferric chloride powder is (200-230): (8-10): (1-3).
MoO when the mass ratio of the sulfur source to the molybdenum source is too low 3 Incomplete vulcanization is easy to generate intermediate products, so that the molybdenum disulfide film is discontinuous, smaller in size and uneven in thickness; if the mass ratio of the sulfur source to the molybdenum source is too high, excessive sulfur vapor is easy to form molybdenum disulfide particles to deposit on the surface of the molybdenum disulfide film, so that the surface of the product is uneven.
The introduction of ferrous chloride is helpful for the formation of parallel steps on the surface of the sapphire substrate and the nucleation and growth of molybdenum disulfide with consistent domain orientation. When the content of ferrous chloride is too low, the prepared molybdenum disulfide is randomly oriented, and the molybdenum disulfide film obtained by splicing is a polycrystalline film; when the content of ferrous chloride is too high, the prepared molybdenum disulfide is a multilayer nano-sheet, and domain orientations are randomly distributed.
Further, it is preferable that the sulfur source is 200 to 230mg in weight, the molybdenum source is 8 to 10mg in weight, and the ferric chloride powder is 1 to 3mg in weight.
In some embodiments, the predetermined temperature of the first temperature zone is 190-230 ℃, the predetermined temperature of the second temperature zone is 900-910 ℃, and the predetermined temperature of the third temperature zone is 900-910 ℃.
If the preset temperature is too low, the volatilization amounts of the sulfur source, the molybdenum source and the ferrous chloride are too low, so that nucleation points on the substrate are fewer, a large-area molybdenum disulfide film cannot be formed, if the preset temperature is too high, the gas phase concentration of the reactant is too high, so that excessive nucleation points on the substrate are caused, molybdenum disulfide tends to vertically grow, and dispersed and multilayer molybdenum disulfide crystals are easy to prepare.
In some embodiments, the distance between the sulfur source and the molybdenum source is 8-10 cm;
and/or the distance between the molybdenum source and the sapphire substrate is 1-3 cm.
In a preferred embodiment, the sulfur source is placed in a first open container, the mixture of the molybdenum source and the ferrous chloride powder is placed in a second open container, the distance between the first open container and the second open container is 8-10 cm, the distance between the second open container and the sapphire substrate is 1-3 cm, and the high-quality two-dimensional single crystal molybdenum disulfide film can be rapidly prepared in the distance range.
In some embodiments, the sulfur source comprises sulfur powder;
and/or the molybdenum source comprises molybdenum trioxide powder.
In some embodiments, the single crystal molybdenum disulfide is grown for a period of time ranging from 5 to 60 minutes.
The growth time is too short, the size of the generated monocrystal molybdenum disulfide is too small, the formation of a continuous two-dimensional molybdenum disulfide film is not facilitated, nucleation points are increased to some extent along with the extension of the growth time, grain boundaries are reduced, the film forming area is increased, and the growth time is too long, so that the molybdenum disulfide is possibly deposited along the vertical direction, and the thickness of the film is too large.
In some embodiments, the carrier gas has a flow rate of 60 to 80sccm.
The flow rate of the carrier gas can further influence the quality of the molybdenum disulfide film, if the flow rate of the carrier gas is too low, the deposition process is too slow, if the flow rate of the carrier gas is too high, the concentration of sulfur vapor in the third temperature zone is too high, and volatilization of a molybdenum source can be inhibited after the concentration reaches a certain degree, so that the density of nucleation points on a substrate is reduced, the triangular monocrystal size is too large, and continuous large-area two-dimensional molybdenum disulfide film is not formed easily.
In some embodiments, the placing of the sapphire substrate is preceded by:
and removing impurities on the surface of the sapphire substrate.
Is beneficial to reducing nucleation sites of molybdenum disulfide on the surface of the sapphire.
Specifically, the method for removing impurities on the surface of the sapphire substrate by ultrasonic cleaning can comprise the following steps:
and sequentially placing the sapphire substrate in deionized water, ethanol and acetone for ultrasonic cleaning for 10 minutes, and then drying by nitrogen to finish cleaning the sapphire substrate.
In some embodiments, prior to passing the carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone, the method of preparing further comprises:
and vacuumizing the first temperature zone, the second temperature zone and the third temperature zone to below 5 Pa.
Further, before the preparation of the molybdenum disulfide crystal, the method further comprises the following steps:
cleaning a reaction cavity of a three-temperature-zone tubular furnace vapor deposition system: and vacuumizing the reaction cavity to below 5Pa, introducing carrier gas, cleaning the reaction cavity for 30min, and removing residual air in the reaction cavity to avoid influencing the quality of the molybdenum disulfide film.
Further, the carrier gas is a protective atmosphere, such as argon.
In some embodiments, after the growth of the single crystal molybdenum disulfide is finished, stopping introducing the carrier gas, and cooling the first temperature region, the second temperature region and the third temperature region to room temperature to obtain the large-size single crystal molybdenum disulfide.
The application is doped with ferrous chloride and matched with a sapphire substrate, so that the large-size two-dimensional monocrystalline molybdenum disulfide film with the wafer level of 4 inches can be efficiently prepared, and the application can be applied to high-performance electronic devices.
The application is further illustrated by the following examples.
Example 1
101: four inches of commercial corner cut-free C-side sapphire substrate was cut to 10cm x 2 cm and placed in deionized water, ethanol and acetone in sequence for 10 minutes of ultrasonic cleaning, and after the cleaning was completed, blow-dried with nitrogen.
102: in a three-temperature-zone high-temperature tube furnace, sequentially placing 200 mg of sulfur powder in a first temperature zone, uniformly mixing 8 mg of molybdenum trioxide powder and 1 mg of ferrous chloride powder according to the sequence from the upstream to the downstream of a gas route, placing the two in a second temperature zone together, and placing a cleaned sapphire substrate in a third temperature zone, wherein the distance between a molybdenum trioxide/ferrous chloride mixture and the sulfur powder is 9 cm, and the distance between the molybdenum trioxide/ferrous chloride mixture and the sapphire substrate is 2 cm;
103: firstly vacuumizing a reaction cavity of a tubular furnace to below 5Pa, then introducing argon with the flow of 500sccm into the reaction cavity, cleaning the reaction cavity, and removing residual air in the cavity for 30 minutes;
104: and (3) raising the temperature of the first temperature region to 200 ℃, raising the temperature of the second temperature region to 900 ℃, raising the temperature of the third temperature region to 900 ℃, introducing argon (70 sccm), carrying out heat preservation reaction for 60min, and naturally cooling after the reaction is finished to obtain the molybdenum disulfide film.
Example 2
The majority of the operating steps of example 1 were included, differing only in:
the incubation time was 5min.
Example 3
The majority of the operating steps of example 1 were included, differing only in:
the incubation time was 15min.
Example 4
The majority of the operating steps of example 1 were included, differing only in:
the incubation time was 30min.
Example 5
The majority of the operating steps of example 1 were included, differing only in:
the incubation time was 50min.
Referring to fig. 1-5, fig. 1-5 show optical microscopic images of molybdenum disulfide prepared in examples 1-5, and it can be seen from the figures that the domains of the molybdenum disulfide nanosheets obtained in examples 1-5 for different growth times are aligned uniformly, and the coverage of molybdenum disulfide increases with the extension of the growth time, as shown in fig. 1, when the growth time is extended to 60min, a 4-inch molybdenum disulfide film can be prepared.
Referring to fig. 6, fig. 6 shows an atomic force microscope image of molybdenum disulfide prepared in example 1, and it can be seen from fig. 6 that the thickness of the large-sized single crystal molybdenum disulfide thin film prepared in example 1 is 0.9nm, which indicates that the prepared molybdenum disulfide is a single-layer two-dimensional sample.
Referring to fig. 7, fig. 7 shows raman spectrum characterization of the molybdenum disulfide thin film prepared in example 1, and it can be seen from fig. 7 that raman spectrum characterization results show that positions of raman characteristic peaks obtained along different directions of the four-inch single-layer molybdenum disulfide thin film are not changed, which indicates that the prepared four-inch single-layer molybdenum disulfide has very high layer number uniformity and crystal quality.
Referring to fig. 8-9, fig. 8-9 show a result of a transmission electron microscope characterization of molybdenum disulfide on a copper mesh, and a molybdenum disulfide/copper mesh sample preparation process includes the following steps: and spin-coating a polymethyl methacrylate polymer support film (the thickness of the polymer film is 500 nanometers) on the surface of the sapphire substrate on which the molybdenum disulfide film grows, heating and baking at 180 ℃ for 10 minutes, then placing the sapphire substrate into a sodium hydroxide etching solution for etching the growth substrate for 10 minutes, fishing out a polymethyl methacrylate polymer film/molybdenum disulfide sample by using a copper mesh, baking at 100 ℃ for 10 minutes to enable the sample to fully contact with the copper mesh, and finally placing the polymethyl methacrylate polymer film/molybdenum disulfide/copper mesh into acetone to remove the support film (the time is 30 minutes) to obtain the molybdenum disulfide/copper mesh sample.
The molybdenum disulfide/copper mesh sample is subjected to transmission electron microscope characterization, as shown in fig. 8, which shows that the thickness of the molybdenum disulfide nano-sheet provided by the application is uniform. Fig. 9 shows an electron diffraction pattern at the splice location of two molybdenum disulfide nanoplatelets, with only one set of six-fold symmetric diffraction spots shown, indicating that the two molybdenum disulfide nanoplatelets have a uniform domain orientation.
Referring to fig. 10, fig. 10 shows a dual-spherical aberration correction scanning transmission electron microscope image of molybdenum disulfide on a copper mesh according to an embodiment of the present application, and the preparation of a molybdenum disulfide/copper mesh sample is described above and will not be described herein.
The molybdenum disulfide/copper mesh sample is subjected to double-spherical-aberration correction scanning transmission electron microscope characterization, as shown in fig. 10, and the result shows that no domain grain boundary is generated at the splicing position of the molybdenum disulfide nano-sheets, which indicates that the molybdenum disulfide nano-sheets with consistent domain orientation can be formed into a single crystal film through atomic-level seamless splicing.
Referring to fig. 11, fig. 11 shows low-energy electron diffraction patterns of 9 different positions randomly selected on the surface of a single molybdenum disulfide sample provided by the embodiment of the application, and it can be seen that the characterization result only shows one set of diffraction spots, which indicates that a single-layer molybdenum disulfide nano-sheet forms a single crystal film by splicing.
Referring to fig. 12, fig. 12 shows the optical microscope characterization result before and after oxygen etching of the molybdenum disulfide sample provided by the embodiment of the application, wherein the left side is an optical microscope characterization comparison chart before and after oxygen etching of the molybdenum disulfide film, and the right side is an optical microscope characterization comparison chart before and after oxygen etching of the molybdenum disulfide nanosheets, and as can be seen from the figures, no obvious change exists on the surface of the sample no matter whether the molybdenum disulfide nanosheets or the molybdenum disulfide film is subjected to oxygen etching, which indicates that the quality of single crystal molybdenum disulfide is good.
Referring to fig. 13 (a) - (b), fig. 13 (a) - (b) illustrate performance testing of a molybdenum disulfide sample applied to an electronic device according to an embodiment of the present application, wherein the testing process includes: transferring the molybdenum disulfide film to a silicon dioxide/silicon substrate, spin-coating ultraviolet photoresist (with the thickness of 200 nanometers) on the surface of the molybdenum disulfide film, and then placing the molybdenum disulfide film on a heating table for drying treatment (the temperature is 115 ℃ and the time is 1 minute); exposing the sample by using an ultraviolet photoetching instrument, wherein the exposure time is set to be 450 milliseconds; and then placing the exposed sample in a developing solution for developing for 3-5 seconds, quickly taking out, cleaning with deionized water, and drying with nitrogen. Respectively evaporating 5-nanometer chromium and 70-nanometer gold on a sample by using a thermal evaporator; finally, carrying out ultrasonic treatment on the evaporated sample for 5-10 minutes to obtain the molybdenum disulfide electronic device.
The transfer characteristic curve test of the molybdenum disulfide electronic device is shown in fig. 13 (a), and the result shows that the monocrystalline molybdenum disulfide film provided by the application is appliedThe on-off ratio in the electronic device can reach 10 8 The electron mobility can reach 86cm 2 /(V·s)。
The output characteristic curves of the molybdenum disulfide electronic devices under different gate voltages are tested, as shown in fig. 13 (b), and the results show that the source current increases linearly with the increase of the source voltage, which indicates that perfect ohmic contact is formed between the single-layer molybdenum disulfide and the electrode.
Referring to fig. 14 (a) - (b), fig. 14 (a) - (b) show performance tests of the molybdenum disulfide thin film applied to a field effect transistor, wherein the test method comprises: the field effect transistor was constructed by randomly selecting 20 samples at different positions on the 4-inch molybdenum disulfide film prepared in example 1, and testing the characteristic transfer curve and the current switching ratio of the field effect transistor respectively, wherein the characteristic transfer curve of the field effect transistor constructed by the molybdenum disulfide film at different positions is close as shown in fig. 14 (a), which shows that the transistor performance is consistent, and the current switching ratio and the electron mobility of the field effect transistor constructed by the molybdenum disulfide film at different positions are respectively concentrated at 10 as shown in fig. 14 (b) 6 ～10 8 And 40-86 cm 2 and/(V.s), the molybdenum disulfide film prepared by the application has excellent electronic device performance.
In combination, the method can prepare the two-dimensional monocrystalline molybdenum disulfide film without domain grain boundary, and the two-dimensional monocrystalline molybdenum disulfide film shows ultrahigh electronic device performance and uniformity, thereby laying a material foundation for further application research and development of integrated circuits and high-end general chips.
Comparative example 1
The majority of the operations including example 1 differ only in that:
no ferric chloride powder was added.
Fig. 15 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 1, and it can be seen from the figure that the domain orientations of the obtained molybdenum disulfide nanoplatelets are randomly distributed without adding ferrous chloride.
Comparative example 2
The majority of the operations including example 1 differ only in that:
the temperature of the first temperature zone was raised to 200 ℃, the temperature of the second temperature zone was raised to 900 ℃, and the temperature of the third temperature zone was raised to 1000 ℃.
Fig. 16 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 2, and it can be seen from the figure that the obtained molybdenum disulfide is a multi-layered nano-sheet and domain orientations are randomly distributed when the growth temperature is too high.
Comparative example 3
The majority of the operations including example 1 differ only in that:
the temperature of the first temperature zone was raised to 200 ℃, the temperature of the second temperature zone was raised to 900 ℃, and the temperature of the third temperature zone was raised to 800 ℃.
Fig. 17 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 3, and it can be seen from the figure that when the growth temperature is too low, the size of the obtained molybdenum disulfide domains is small, and the domain orientations are randomly distributed.
Comparative example 4
The majority of the operations including example 1 differ only in that:
ferrous oxide powder is used to replace ferrous chloride powder.
Fig. 18 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 4, and it can be seen from the figure that the domain orientations of the obtained molybdenum disulfide nanosheets are randomly distributed after ferrous chloride is replaced with ferrous oxide.
Comparative example 5
The majority of the operations including example 1 differ only in that:
a silicon substrate was used instead of a sapphire substrate.
Fig. 19 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 5, and it can be seen from the figure that the domain orientations of the obtained molybdenum disulfide nanoplatelets are randomly distributed after using a silicon substrate instead of a sapphire substrate.
Comparative example 6
The majority of the operations including example 1 differ only in that:
the addition amount of the ferric chloride powder was 0.5 mg.
Fig. 20 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 6, and it can be seen from the figure that the domain orientations of the obtained molybdenum disulfide nanosheets are randomly distributed when the content of ferrous chloride is too low.
Comparative example 7
The majority of the operations including example 1 differ only in that:
the addition amount of the ferric chloride powder was 5 mg.
Fig. 21 shows an optical microscopic image of the molybdenum disulfide sample prepared in comparative example 7, and it can be seen from the figure that when the content of ferrous chloride is too high, the obtained molybdenum disulfide is a multilayer nano-sheet, and domain orientations are randomly distributed.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The preparation method of the large-size single-crystal molybdenum disulfide is characterized by comprising the following steps of:
placing a sulfur source in a first temperature zone, placing a molybdenum source and ferrous chloride powder in a second temperature zone, and placing a sapphire substrate in a third temperature zone;
passing a carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone in sequence;
heating the first temperature zone, the second temperature zone and the third temperature zone to respective preset temperatures to grow single-crystal molybdenum disulfide;
the mass ratio of the sulfur source to the molybdenum source to the ferric chloride powder is (200-230): (8-10): (1-3);
the preset temperature of the first temperature zone is 190-230 ℃, the preset temperature of the second temperature zone is 900-910 ℃, and the preset temperature of the third temperature zone is 900-910 ℃;
the distance between the sulfur source and the molybdenum source is 8-10 cm;
and/or the distance between the molybdenum source and the sapphire substrate is 1-3 cm.
2. The method of producing large-size single crystal molybdenum disulfide according to claim 1, wherein the sulfur source comprises sulfur powder;
and/or the molybdenum source comprises molybdenum trioxide powder.
3. The method for producing large-size single crystal molybdenum disulfide according to claim 1, wherein the growth time of the single crystal molybdenum disulfide is 5 to 60 minutes.
4. The method for producing large-sized single crystal molybdenum disulfide according to claim 1, wherein the flow rate of the carrier gas is 60 to 80sccm.
5. The method for preparing large-sized single crystal molybdenum disulfide according to claim 1, further comprising, before placing the sapphire substrate:
and removing impurities on the surface of the sapphire substrate.
6. The method of producing large size single crystal molybdenum disulfide according to claim 1, wherein prior to passing the carrier gas through the first temperature zone, the second temperature zone, and the third temperature zone, the method further comprises:
and vacuumizing the first temperature zone, the second temperature zone and the third temperature zone to below 5 Pa.
7. The method for producing large-size single-crystal molybdenum disulfide according to claim 1, wherein after the growth of single-crystal molybdenum disulfide is completed, the introduction of carrier gas is stopped, and the first temperature zone, the second temperature zone and the third temperature zone are cooled to room temperature, to obtain the large-size single-crystal molybdenum disulfide.
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