CN115058699A - Monolayer molybdenum disulfide based on chemical vapor deposition and preparation method thereof - Google Patents
Monolayer molybdenum disulfide based on chemical vapor deposition and preparation method thereof Download PDFInfo
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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
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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
- C23C16/44—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
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
Abstract
The invention discloses a monolayer molybdenum disulfide based on chemical vapor deposition and a preparation method thereof, wherein the preparation method comprises the following steps: selecting a substrate; weighing appropriate amount of MoO 3 Powder is filled into a quartz sleeve with an opening at one end; a substrate and a substrate filled with MoO 3 Placing a quartz sleeve of the powder in a tube furnace, vertically placing a substrate on one side of an opening of the quartz sleeve, wherein the opening faces to the surface of the substrate; weighing a proper amount of sulfur powder, placing the sulfur powder on one side of the air inlet end of the tube furnace, and mixing the sulfur powder with MoO 3 The powders are separated by a proper distance; adding MoO 3 Heating the powder to MoO 3 Evaporating the powder; moving the sulfur powder to near the middle of the tube furnace to evaporate the sulfur powder and mix with the MoO 3 Carrying out powder steam reaction; health-care productFor a predetermined time to deposit a large area monolayer of MoS on the substrate surface 2 . The invention uses a quartz sleeve with an opening at one end to contain MoO 3 And (3) powder, and meanwhile, the growth substrate is vertically placed with the airflow direction to reduce the concentration gradient of the substrate surface, so that the growth of centimeter-level single-layer molybdenum disulfide is realized.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to single-layer molybdenum disulfide based on chemical vapor deposition and a preparation method thereof.
Background
Two-dimensional transition metal chalcogenides (TMDs) are attracting much attention due to excellent optical and electrical properties such as thickness at the atomic level, unique layered structure, band gap width in the visible light range, and the like. Molybdenum disulfide is taken as a typical transition metal chalcogenide, the band gap width can be adjusted between 1.4-1.9eV along with the number of layers, and meanwhile, molybdenum disulfide has good air stability and can keep the stability of various properties in the air atmosphere for a long time, so that molybdenum disulfide is considered as an application material of a new generation of microelectronic, optoelectronic and flexible electronic devices. However, the preparation of large-area single-layer molybdenum disulfide is still challenging at present — Metal Organic Chemical Vapor Deposition (MOCVD) requires complex equipment and high environmental cost; the mechanical stripping method requires manual operation and is difficult to realize scale production, and the Chemical Vapor Deposition (CVD) method is widely researched as an ideal controllable and expandable two-dimensional material growth method.
Referring to fig. 1, fig. 1 is a schematic diagram of molybdenum disulfide growth by a conventional back-off method. The most typical growth method of the monolayer molybdenum disulfide is solid powder MoO 3 The powder and the sulfur powder are respectively used as a Mo source and an S source and are placed in a chamber filled with SiO 2 Tube furnace for Si substrate (reverse-buckled method) and argon Ar gas introduction 2 As a carrier gas. During the growth process, solid MoO 3 The powder and the sulphur powder are first evaporated into gaseous precursors and subsequently reacted with each other in a growth chamber to produce gaseous MoS 2 The crystal nuclei are deposited on the downstream substrate with the aid of the carrier gas flow and grow further to form crystal grains.
However, such a conventionIn the method for growing solid powder, MoO is generated from the solid powder 3 Exposure in a tube furnace is prone to two problems: (1) MoO 3 The solid powder has limited mass, and the concentration of Mo precursor can follow MoO in the growth process 3 The powder spends time and decreases; (2) the metal source powder exposed and placed in the reaction process is easily reduced into refractory molybdenum dioxide by the sulfuration of gaseous sulfur vapor and covered on MoO 3 Surface, causing a reduction or even termination of the supply of the metal source. These two problems cause the metal source to be exposed in such a manner that the supply of the metal precursor is insufficient or terminated at the end of growth, thereby causing difficulty in the growth of crystal nuclei. In addition, because the substrate is horizontally (reversely) placed, the transition metal precursor reaches the surface of the substrate through evaporation, and because of the non-uniformity of carrier gas diffusion and the occurrence of adsorption and growth of the substrate, a concentration gradient of the Mo precursor along the airflow direction is formed on the surface of the substrate, so that the S/Mo concentration ratio of the surface of the substrate is unbalanced, and further different areas of the surface of the substrate show different layers of molybdenum disulfide growth. Typically, a monolayer of molybdenum disulfide grown from conventional solid state powders is present only in the micron range region at the edge of the substrate. The uneven supply of the metal precursor and the existence of the concentration gradient on the surface of the substrate make the growth of large-area single-layer molybdenum disulfide still difficult, and the development of a simple, convenient and economic large-area molybdenum disulfide growth process is urgently needed.
Disclosure of Invention
In order to solve the problem that a large-area monolayer molybdenum disulfide material is difficult to grow in the prior art, the invention provides monolayer molybdenum disulfide based on chemical vapor deposition and a preparation method thereof. The technical problem to be solved by the invention is realized by the following technical scheme:
one aspect of the invention provides a preparation method of monolayer molybdenum disulfide based on chemical vapor deposition, which comprises the following steps:
s1: selecting a substrate and cleaning the substrate;
s2: weighing appropriate amount of MoO 3 Powder is filled into a quartz sleeve with an opening at one end;
s3: the substrate is provided with MoO 3 A quartz sleeve of powder is placed in the middle of the tube furnace, the substrate is vertically placed on one side of an opening of the quartz sleeve, and the opening of the quartz sleeve faces to the surface of the substrate;
s4: weighing a proper amount of sulfur powder, placing the sulfur powder on one side of the air inlet end of the tube furnace, and mixing the sulfur powder with the MoO 3 The powders are separated by a proper distance;
s5: sealing the tube furnace and reacting the MoO under protective gas 3 Heating the powder to 750-850 ℃ to enable MoO 3 Evaporating the powder;
s6: moving the sulfur powder to near the middle of the tube furnace to evaporate the sulfur powder and mix with the MoO 3 Carrying out powder steam reaction;
s7: preserving the heat for a preset time at 750-850 ℃ to deposit large-area single-layer MoS on the surface of the vertically placed substrate 2 。
In an embodiment of the present invention, the S1 includes:
selecting and cutting a substrate into a proper size, sequentially putting the substrate into deionized water, acetone and isopropanol to perform ultrasonic cleaning for 10-15 min, washing for 1-3 times by using the deionized water, and finally drying the surface of the substrate by using a nitrogen gun.
In an embodiment of the present invention, the S2 includes:
weighing 1-5 mg of MoO 3 And putting the powder into a quartz sleeve with the diameter of 5-8 mm and an opening at one end.
In an embodiment of the present invention, the S3 includes:
will be filled with MoO 3 Putting a quartz sleeve of powder into the middle part of a corundum boat, and vertically placing the substrate on one side of the corundum boat to enable an opening of the quartz sleeve to face the surface of the substrate; then will contain MoO 3 A corundum boat of powder and substrate is placed inside the hearth of the tube furnace.
In one embodiment of the invention, the MoO 3 The distance between the powder and the surface of the substrate is 10-20 mm.
In an embodiment of the present invention, the S4 includes:
weighing 50-200 mg of sulfur powder, putting the sulfur powder into a quartz boat, putting the quartz boat into a quartz sleeve with a magnet, putting the quartz sleeve with the magnet on one side of the air inlet end of the tube furnace, and enabling the sulfur powder and MoO 3 The spacing between the powders is greater than 25 cm.
In an embodiment of the present invention, the S5 includes:
sealing a reaction cavity of the tubular furnace, and filling 500-1000 sccm of argon to purge the reaction cavity for 30-120 min;
continuously purging with argon, and heating the tube furnace at 25-30 deg.C/min to make MoO 3 Rapidly heating the powder to 650-700 ℃;
reducing the temperature rise rate to 15 ℃/min, reducing the argon flow to 50-100 sccm, and continuing to heat until the central temperature of the furnace body reaches 750-850 ℃ so as to enable MoO 3 The powder was evaporated.
In an embodiment of the present invention, the S6 includes:
the quartz sleeve with the magnet is controlled by an external magnet to move so as to move the quartz boat filled with the sulfur powder towards the hearth, so that the sulfur powder center and the MoO 3 The powder center-to-center spacing is reduced to reach the vaporization temperature of the sulfur powder.
In an embodiment of the present invention, the S7 includes:
keeping the temperature at the growth temperature of 750-850 ℃ for 5-20 min to deposit and grow large-area single-layer MoS on the surface of the vertically placed substrate 2 。
In another aspect, the invention provides a monolayer of molybdenum disulfide based on chemical vapor deposition, which is prepared by the preparation method described in any one of the above embodiments.
Compared with the prior art, the invention has the beneficial effects that:
1. based on the reasons of the concentration decrease of the metal powder source along with the time and the concentration gradient of the substrate surface which are caused by the traditional CVD back-off growth of the solid powder source, the preparation method of the invention provides that a small-diameter sleeve with an opening at one end is used for containing MoO 3 Powder, and placing the growth substrate perpendicular to the gas flow direction to reduce the concentration on the surface of the substrateThe growth of centimeter-level single-layer molybdenum disulfide is successfully realized through gradient. The molybdenum disulfide crystal domain grown by the method has large size, and the average grain size can reach 15 mu m and can reach 70 mu m at most.
2. The preparation method protects MoO through a small-diameter sleeve with an opening at one end 3 The powder is prevented from being vulcanized and reduced by sulfur vapor in the reaction growth stage, and MoO is guaranteed 3 The stability and uniformity of the metal source supplied by the powder can be obviously controlled by controlling the distance between the protective sleeve and the surface of the substrate, and the controllability of the CVD preparation is greatly improved.
3. The area of the monolayer molybdenum disulfide grown by the preparation method can cover the whole growth substrate, the growth of the centimeter-level monolayer molybdenum disulfide with the thickness of 13mm multiplied by 13mm is realized, the applicability is good, and the operation is simple and convenient.
4. The preparation method of the invention does not need to transform the tube furnace device, is different from other complicated precursor supply modes designed for large-area molybdenum disulfide growth, does not need to design a complicated growth control device, and only uses a small-diameter sleeve with an opening at one end to protect the metal powder source from being vulcanized by sulfur vapor in the growth process so as to ensure the stable supply of the metal precursor in the growth process.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic diagram of a conventional back-off process for growing molybdenum disulfide;
FIG. 2 is a flow chart of a method for preparing monolayer molybdenum disulfide based on chemical vapor deposition according to an embodiment of the present invention;
FIG. 3 is a schematic view of a single-layer molybdenum disulfide manufacturing apparatus according to an embodiment of the present invention;
FIG. 4 is a top view of a placement position within a quartz boat in accordance with an embodiment of the present invention;
FIG. 5 is a picture of a substrate surface prepared using a method of an embodiment of the invention and using a conventional back-off process;
FIG. 6 is an optical microscope photograph of a large area monolayer of molybdenum disulfide grown using a method of preparation according to an embodiment of the invention;
FIG. 7 is a multi-angle large-area two-dimensional corner optical microscope image of transfer stack after growing large-area single-layer molybdenum disulfide by the growth process of example two;
FIG. 8 is an optical microscope photograph of a monolayer of molybdenum disulfide prepared under varying argon gas flow conditions;
FIG. 9 is an optical microscope image of a single layer of molybdenum disulfide prepared under varying Mo source quality conditions;
figure 10 is an optical microscope image of a monolayer of molybdenum disulfide prepared under different diffusion distance conditions.
Description of reference numerals:
1-a substrate; 2-MoO 3 Powder; 3-quartz sleeve; 4-corundum boat; 5-a tube furnace; 6-sulfur powder; 7-quartz boat.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, a chemical vapor deposition based single-layer molybdenum disulfide and a preparation method thereof according to the present invention are described in detail below with reference to the accompanying drawings and the detailed description.
The foregoing and other technical matters, features and effects of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings. The technical means and effects of the present invention adopted to achieve the predetermined purpose can be more deeply and specifically understood through the description of the specific embodiments, however, the attached drawings are provided for reference and description only and are not used for limiting the technical scheme of the present invention.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or device that comprises a list of elements does not include only those elements but may include other elements not expressly listed. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element.
Example one
Referring to fig. 2 to 4, fig. 2 is a flow chart of a method for preparing single-layer molybdenum disulfide based on chemical vapor deposition according to an embodiment of the present invention, fig. 3 is a schematic view of an apparatus for preparing single-layer molybdenum disulfide according to an embodiment of the present invention, and fig. 4 is a top view of a position for placing a quartz boat according to an embodiment of the present invention. The preparation method of this example includes:
s1: the substrate 1 is picked up and the substrate 1 is cleaned.
The substrate 1 includes, but is not limited to, a silicon/silicon dioxide substrate, a sapphire substrate, a mica substrate, or a polycarbonate Plate (PC) substrate, etc. Cutting the selected substrate into 13mm, sequentially putting the substrate into a beaker with deionized water, acetone and isopropanol for ultrasonic cleaning for 10-15 min, lightly washing with deionized water, and finally blowing water drops on the surface of the substrate with a nitrogen gun. A silicon/silicon dioxide substrate is preferred.
S2: selecting a proper amount of MoO 3 The powder 2 is loaded into a quartz sleeve 3 which is open at one end.
Specifically, 1-5 mg of MoO is weighed 3 The powder 2 is put into a quartz sleeve 3 with a diameter of 5-8 mm and an opening at one end.
Preferably, the quartz sleeve 3 has an outer diameter of 8mm and an inner diameter of 5 mm.
S3: a substrate 1 and a substrate filled with MoO 3 The quartz sleeve 3 of the powder 2 is placed in the middle of the tube furnace 4, and the substrate 1 is placed vertically on the side of the opening of the quartz sleeve 3, the opening of the quartz sleeve 3 facing the surface of the substrate 1.
Specifically, will contain MoO 3 The quartz sleeve 3 of the powder 2 is placed in the middle of a corundum boat 4, after which the substrate 1 is placed vertically on one side of the corundum boat 4 with the opening of the quartz sleeve 3 facing the surface of the substrate 1, MoO 3 The distance between the powder 2 and the substrate 1 is 10-20 mm; finally, MoO is placed 3 Of powder 2 and substrate 1The corundum boat 4 is placed in the hearth of the tube furnace 5.
S4: weighing a proper amount of sulfur powder 6, placing the sulfur powder on one side of the air inlet end of the tubular furnace 5, and keeping a proper distance from the hearth of the tubular furnace 5.
Weighing 50-200 mg of sulfur powder 6 into a quartz boat 7, placing the quartz boat 7 into a quartz sleeve with a magnet (not shown in the figure), placing the quartz sleeve with the magnet on the side of the air inlet end of the tube furnace, and enabling the sulfur powder 6 and MoO 3 The spacing between the powders 2 is greater than 25 cm.
S5: sealing the tube furnace 5, and adding MoO under the condition of protective gas 3 Heating the powder 2 to 750-850 ℃ to ensure that MoO is generated 3 The powder was evaporated.
Specifically, a reaction cavity of the tubular furnace is sealed, 500-1000 sccm of argon gas is filled into the reaction cavity, the reaction cavity is purged for 30-120 min to remove air in the cavity and purify the atmosphere of the cavity, and it is noted that, as shown in fig. 3, the purging direction of the argon gas is from the side where the sulfur powder 6 is placed to the side where the MoO is placed 3 One side of the powder 2 and then blown against the surface of the substrate 1; continuously purging with argon, and heating the tube furnace at 25-30 deg.C/min to make MoO 3 Rapidly heating the powder to 650-700 ℃; then, the temperature rise rate is reduced to 15 ℃/min, the argon flow is reduced to 50-100 sccm, and the furnace is continuously heated until the central temperature of the furnace body reaches 750-850 ℃, so that MoO is obtained 3 Evaporation of powder 2 to MoO 3 And (4) steam.
S6: moving the sulfur powder to near the middle of the tube furnace to evaporate the sulfur powder and mix with the MoO 3 The powder steam reacts.
Specifically, the quartz sleeve with the magnet is controlled by an external magnet to move the quartz boat 7 filled with the sulfur powder 6 toward the hearth, so that the center of the sulfur powder 6 and the MoO 3 The distance between the centers of the powder 2 is reduced to reach the evaporation temperature of the sulfur powder 6 (the sulfur powder is heated to 130-180 ℃ and then evaporated), and in this embodiment, the distance is moved to the center of the sulfur powder and the MoO 3 The distance between the centers of the powders is 20-21 cm, and because the powder is closer to a heating area of a hearth, the sulfur powder 6 is heated to the evaporation temperature and is evaporated into sulfur steam.
S7: keeping the temperature for a predetermined time at 750-850 ℃ to be on the vertically placed substrate surfaceSurface deposition of large area single layer MoS 2 。
Specifically, the temperature is kept for 5-20 min at the growth temperature of 750-850 ℃, so that sulfur steam reaches the surface of the substrate under the drive of Ar airflow and MoO 3 Vapor and reaction are carried out, and large-area single-layer MoS is deposited and grown on the surface of the vertically placed substrate 2 。
Further, the preparation method of this embodiment further includes:
s8: naturally cooling to 300-500 ℃, opening the furnace cover to rapidly cool, taking out the substrate vertically placed in the corundum boat when the temperature of the tube furnace is reduced to 25-80 ℃, and finishing the growth process; the quartz sleeve, corundum boat, quartz boat, and tube furnace chamber were then cleaned.
Referring to fig. 5, fig. 5 is a picture of the substrate surface prepared by the method of the embodiment of the present invention (left) and the conventional back-off method (right), and it can be found that the arc-shaped concentration gradient appears on the substrate surface by the conventional growth method, and the substrate surface prepared by the preparation method of the embodiment of the present invention presents a uniform color, which indicates that the precursor concentration on the substrate surface is kept uniform during the growth process.
Referring to fig. 6, fig. 6 is an optical microscope image of a large-area monolayer of molybdenum disulfide grown by the preparation method of the embodiment of the invention, wherein the left image shows the large-area uniformity of the substrate surface, and the right image shows that the domain size is about 15 μm.
The preparation method of this example provides for MoO to be contained using a small diameter sleeve with one open end 3 And (3) powder, and meanwhile, the growth substrate is vertically placed with the airflow direction to reduce the concentration gradient of the substrate surface, so that the growth of centimeter-level single-layer molybdenum disulfide is successfully realized. The prepared large-area molybdenum disulfide material is beneficial to the preparation of two-dimensional field effect transistors, photoelectric devices and sensors and the characterization of characteristics of the molybdenum disulfide material or any related research related to the molybdenum disulfide material.
Example two
On the basis of the above embodiments, this embodiment proposes another preparation method of large-area monolayer molybdenum disulfide, which includes the following steps:
step 1: selecting SiO 2 Si substrate and SiO 2 And cleaning the/Si substrate.
Specifically, the cut 13mm × 13mmSiO 2 Putting the Si substrate into a beaker filled with deionized water, acetone and isopropanol in sequence for ultrasonic cleaning for 10min, lightly washing with deionized water, and finally blowing the surface of the substrate with a nitrogen gun.
Step 2: 2mg of MoO 3 Putting the powder into a quartz sleeve with a diameter of 5mm and an opening at one end, putting the quartz sleeve into the middle of a cuboid corundum boat, and treating the surface of the quartz sleeve with SiO 2 the/Si substrate is vertically arranged on one side of the corundum boat, and the substrate is vertically arranged on one side of an opening of a quartz sleeve, the opening of the quartz sleeve faces the surface of the substrate, and MoO is controlled 3 The distance between the powder and the substrate was 1.5 cm.
And step 3: will hold MoO 3 Placing the corundum boat with the substrate in the middle of the tube furnace, placing 150mg of sulfur powder in a quartz boat, and placing the center of the sulfur powder and MoO 3 The distance between the centers of the medicinal powder is about 25cm,
and 4, step 4: and sealing the reaction cavity of the tubular furnace, and purging the reaction cavity of the tubular furnace for 50min by using 500sccm of argon gas to remove air in the cavity and purify the atmosphere of the cavity.
And 5: continuously purging with argon, and heating the tube furnace at 30 deg.C/min to make MoO 3 The powder is quickly heated to 650 ℃; then reducing the temperature rise rate to 15 ℃/min, reducing the argon flow to 100sccm, and continuing heating until the central temperature of the furnace body reaches 800 ℃ so as to ensure that MoO 3 Evaporation of powder 2 to MoO 3 Steam; when the central temperature of the furnace body reaches 800 ℃, the quartz tube with the magnet is controlled by an external magnet to move a reaction temperature zone of the quartz boat filled with the sulfur powder, so that the sulfur powder center and the MoO 3 The center of the powder is 20cm away, because closer to the furnace heating zone, the sulfur powder 6 heats up to its evaporation temperature and evaporates into sulfur vapor.
And 6: keeping the temperature at 800 ℃ for 5min to ensure that the sulfur steam reaches the surface of the substrate and is MoO under the drive of Ar gas flow 3 Steam and reaction, on vertically disposed SiO 2 The deposition growth of the silicon substrate surface is largeArea single layer MoS 2 。
The embodiment of the invention provides monolayer molybdenum disulfide based on chemical vapor deposition, which is prepared by using the preparation method in any one of the above embodiments.
Furthermore, the embodiment of the invention also provides a preparation method of the large-area double-layer molybdenum disulfide. Specifically, large-area single-layer MoS is grown in the way 2 After the furnace temperature is cooled, taking out the grown substrate, cutting the substrate into two halves, transferring one half of the molybdenum disulfide material to the other half by using a polyvinyl alcohol (PVA) aqueous solution, namely, overlapping the two sides together, fully attaching the two sides by heating and pressurizing, and then soaking the substrate in deionized water for 15min to remove the PVA film; and then, taking out the soaked stacked substrate, and blow-drying moisture by using a nitrogen gun to obtain the large-area stacked single-layer molybdenum disulfide corner structure, wherein the result is as shown in fig. 7, and the large-area stacked laminated structure of molybdenum disulfide can be clearly seen.
This embodiment grows even individual layer molybdenum disulfide of large tracts of land for the transfer piles up the individual layer molybdenum disulfide corner of a large tracts of land, multi-angle, and traditional two-dimensional corner needs meticulous drawback of piling up one by one can be overcome in this embodiment large tracts of land individual layer molybdenum disulfide's growth, can be simpler, economy, quick pile up out the two-dimensional corner that has different angles, for the research of molybdenum disulfide corner.
EXAMPLE III
On the basis of example two, in this example, the flow rate of argon gas, the mass of Mo source, and the diffusion distance h (i.e., the distance from the substrate surface to the quartz sleeve opening) were set as variables respectively to illustrate the effect of different parameters on the preparation results.
Firstly, the influence of the argon gas flow on the preparation result is studied through experiments, and the mass of 100mg of S powder and 1.5mg of MoO are kept in the experimental process 3 The quality, the substrate placement position and the growth temperature profile were constant. Referring to fig. 8, fig. 8 is an optical microscope image of a monolayer of molybdenum disulfide prepared under different argon gas flow conditions. It can be found that: when the argon gas flow is 30sccm, the nucleation density of the substrate surface is low, and the mass flow is smallThe precursor transported to the surface of the substrate is insufficient, the size of a grown MoS2 crystal domain is smaller than that of a normally grown domain at 6-9 mu m, and meanwhile, more secondary nucleation points are observed to grow, which may be related to the vertical placement of the substrate; when the flow of argon gas is 50sccm, the nucleation density of the surface of the substrate can be seen to be relatively uniform, the domain size is about 15 mu m, and the method is relatively suitable for later-stage application; when the argon gas flow is 70sccm, the grown nucleation density is higher, and the domain size does not obviously change with 50sccm, which can be attributed to the consumption of a precursor by more critical nucleus growth under higher nucleation density; while the irregularities of the domains are more pronounced, it can be seen that the triangular sides of most domains have less curvature, which may be a higher flow rate to shift growth from thermodynamically driven to kinetic, a higher flow rate results in a higher growth rate, which causes the growth rate of the Mo side to that of the sulfur side to be different, and a slower side does not catch up with the faster side to cause domain curvature, which may be more pronounced in higher gas flow (the presence of triangular star shaped domains).
Next, MoO was investigated by experiments 3 The influence of the source on the preparation result is kept constant in the quality (100mg) of the S powder, the gas flow rate (50sccm), the placement position of the substrate and the growth temperature curve in the experimental process, and the precursor MoO is changed 3 Quality of powder to investigate MoO 3 Influence of the source on growth. Referring to fig. 9, fig. 9 is an optical microscope image of a monolayer of molybdenum disulfide prepared under different Mo source quality conditions. The quality of the Mo source is a determining factor for determining the concentration of the Mo precursor, the concentration of the precursor determines the size of the final crystal domain, and the nucleation rate is also influenced to a certain extent. When m is 2.0mg, the larger Mo source mass results in larger Mo precursor concentration, so that the crystal nuclei on the surface of the substrate can grow up smoothly under the transportation of a proper carrier gas rate, and thus, higher nucleation density and tighter domain size distribution can be observed on the surface of the substrate. When m is 1.5mg, the quality of Mo is relatively suitable for growth, the nucleation density of the substrate surface is moderate, and the size of the crystal domain is large (on average, 20 or so long). When m is 1.0mg, the Mo source has a low mass, and the Mo source precursor continuously supplied during growth is insufficient, so that the crystal domain grows to a certain size (7 to 8 μm)) Growth stops and the resulting sample has a relatively small domain size.
Further, in the method of the embodiment of the present invention, the Mo precursor can reach the substrate surface only by diffusion of the carrier gas for a certain transport distance, so that a parameter, i.e., a diffusion distance (h), is set in this embodiment, which represents a distance from the Mo precursor to the substrate surface after overflowing the protective sleeve, and this embodiment also studies the influence of the diffusion distance on the preparation result through experiments, and keeps the mass of the S powder of 100mg, the mass of the MoO3 of 1.5mg, the flow rate of the carrier gas of 50sccm, the placement position of the substrate, and the growth temperature curve unchanged during the experiment. Diffusion distance influencing MoS 2 Diffusion of growth precursor transport, see figure 10, figure 10 is an optical microscope image of a monolayer of molybdenum disulfide prepared at different diffusion distances, and it can be found that: when h is 10mm, the diffusion distance is too short, the distance for conveying the Mo precursor is insufficient, the concentration of the carrier gas conveyed to the surface of the substrate is large, the diffusion is not uniform, and the obvious transverse concentration gradient of the surface of the substrate is caused. When h is 17mm, the nucleation density of the substrate surface is proper, the crystal domains are uniformly distributed, the domain size is proper, and the diffusion distance at the moment is just proper for precursor transportation. When h is 20mm, the control force of carrier gas transport on the precursor is reduced due to the increase of diffusion distance, and it can be seen that nucleation density on the substrate surface is greatly reduced and the domain size is relatively small due to the shortage of the precursor at the time of growth.
In summary, the preparation method of the monolayer molybdenum disulfide based on chemical vapor deposition in the embodiment of the invention provides that a small-diameter sleeve with an opening at one end is used for containing MoO 3 And (3) powder, and meanwhile, the growth substrate is vertically placed in the direction of airflow to reduce the concentration gradient of the surface of the substrate, so that the growth of centimeter-level single-layer molybdenum disulfide is successfully realized. The molybdenum disulfide crystal domain grown by the method has large size, and the average grain size can reach 15 mu m and can reach 70 mu m at most. The area of the monolayer molybdenum disulfide grown by the preparation method of the embodiment can cover the whole growth substrate, the growth of the centimeter-level monolayer molybdenum disulfide with the thickness of 13mm multiplied by 13mm is realized, and the applicability is highGood and simple operation. The preparation method of the embodiment does not need to modify a tube furnace device, is different from other complicated precursor supply modes of large-area molybdenum disulfide growth design, does not need to design a complicated growth control device, and only uses a small-diameter sleeve with an opening at one end to protect a metal powder source from being vulcanized by sulfur vapor in the growth process so as to ensure the stable supply of the metal precursor in the growth process. The small-diameter sleeve with an opening at one end used in the method can control the concentration of the metal precursor through the diffusion distance while protecting the supply stability and uniformity of the metal precursor, thereby greatly improving the controllability of the solid powder source CVD method.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of monolayer molybdenum disulfide based on chemical vapor deposition is characterized by comprising the following steps:
s1: selecting a substrate and cleaning the substrate;
s2: weighing appropriate amount of MoO 3 Powder is filled into a quartz sleeve with an opening at one end;
s3: the substrate and the filled MoO are placed 3 A quartz sleeve of powder is placed in the middle of the tube furnace, the substrate is vertically placed on one side of an opening of the quartz sleeve, and the opening of the quartz sleeve faces to the surface of the substrate;
s4: weighing a proper amount of sulfur powder, placing the sulfur powder on one side of the air inlet end of the tube furnace, and mixing the sulfur powder with the MoO 3 The powders are separated by a proper distance;
s5: sealing the tube furnace and reacting the MoO under protective gas 3 Heating the powder to 750-850 ℃ to enable the MoO 3 Evaporating the powder;
s6: moving the sulfur powder to near the middle of the tube furnace toEvaporating sulfur powder and mixing with MoO 3 Carrying out powder steam reaction;
s7: preserving the heat for a preset time at 750-850 ℃ to deposit large-area single-layer MoS on the surface of the vertically placed substrate 2 。
2. The method according to claim 1, wherein the step S1 comprises:
selecting and cutting a substrate into a proper size, sequentially putting the substrate into deionized water, acetone and isopropanol to perform ultrasonic cleaning for 10-15 min, washing for 1-3 times by using the deionized water, and finally drying the surface of the substrate by using a nitrogen gun.
3. The method according to claim 1, wherein the step S2 comprises:
weighing 1-5 mg of MoO 3 And putting the powder into a quartz sleeve with the diameter of 5-8 mm and an opening at one end.
4. The method for preparing monolayer molybdenum disulfide based on chemical vapor deposition according to claim 1, wherein the step S3 comprises:
will be filled with MoO 3 Putting a quartz sleeve of powder into the middle part of a corundum boat, and vertically placing the substrate on one side of the corundum boat to enable an opening of the quartz sleeve to face the surface of the substrate; then will contain MoO 3 A corundum boat of powder and substrate is placed inside the hearth of the tube furnace.
5. The method of claim 4, wherein the MoO is selected from the group consisting of molybdenum disulfide, and molybdenum disulfide 3 The distance between the powder and the surface of the substrate is 10-20 mm.
6. The method for preparing monolayer molybdenum disulfide based on chemical vapor deposition according to claim 1, wherein the step S4 comprises:
weighing 50-200 mg of sulfur powder, putting the sulfur powder into a quartz boat, putting the quartz boat into a quartz sleeve with a magnet, putting the quartz sleeve with the magnet on one side of the air inlet end of the tube furnace, and enabling the sulfur powder and MoO 3 The spacing between the powders is greater than 25 cm.
7. The method for preparing monolayer molybdenum disulfide based on chemical vapor deposition according to claim 6, wherein S5 comprises:
sealing a reaction cavity of the tubular furnace, and filling 500-1000 sccm of argon to purge the reaction cavity for 30-120 min; continuously purging with argon, and heating the tube furnace at 25-30 deg.C/min to make MoO 3 Rapidly heating the powder to 650-700 ℃; reducing the temperature rise rate to 15 ℃/min, reducing the argon flow to 50-100 sccm, and continuing to heat until the central temperature of the furnace body reaches 750-850 ℃ so as to enable MoO 3 The powder was evaporated.
8. The method according to claim 7, wherein the step S6 comprises:
the quartz sleeve with the magnet is controlled by an external magnet to move so as to move the quartz boat filled with the sulfur powder towards the hearth, so that the sulfur powder center and the MoO 3 The powder center-to-center spacing is reduced to reach the vaporization temperature of the sulfur powder.
9. The method for preparing monolayer molybdenum disulfide based on chemical vapor deposition according to claim 1, wherein the step S7 comprises:
keeping the temperature at the growth temperature of 750-850 ℃ for 5-20 min to deposit and grow large-area single-layer MoS on the surface of the vertically placed substrate 2 。
10. Monolayer molybdenum disulphide based on chemical vapour deposition, characterized in that it is prepared using the preparation method according to any one of claims 1 to 9.
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