CN115323482A - Water-assisted two-dimensional non-layered In 2 S 3 Method of growing - Google Patents

Water-assisted two-dimensional non-layered In 2 S 3 Method of growing Download PDF

Info

Publication number
CN115323482A
CN115323482A CN202210994862.5A CN202210994862A CN115323482A CN 115323482 A CN115323482 A CN 115323482A CN 202210994862 A CN202210994862 A CN 202210994862A CN 115323482 A CN115323482 A CN 115323482A
Authority
CN
China
Prior art keywords
dimensional
quartz tube
gas
layered
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210994862.5A
Other languages
Chinese (zh)
Other versions
CN115323482B (en
Inventor
周喻
邹路玮
范秀莲
李成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202210994862.5A priority Critical patent/CN115323482B/en
Publication of CN115323482A publication Critical patent/CN115323482A/en
Application granted granted Critical
Publication of CN115323482B publication Critical patent/CN115323482B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/002—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/64—Flat crystals, e.g. plates, strips or discs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a water-assisted non-layered two-dimensional In 2 S 3 The growth method comprises the following steps: the method comprises heating indium sulfide powder in Ar carrier gas containing a small amount of water vapor at 800-850 deg.C for volatilization, and performing physical vapor deposition to obtain indium trisulfide single crystal. The invention can effectively reduce In by using the water vapor In the carrier gas for assistance through a simple physical vapor deposition method 2 S 3 The nucleation quantity In the growth process of the single crystal nano-sheet is beneficial to the growth of nano-sheet particles, thereby obtaining the non-layered two-dimensional In 2 S 3 Single crystal sodiumRice flakes, and the prepared nano flakes are thin and have the thickness range of 5-10nm; the size of the single crystal is large, the size range is 20-150 mu m, and the regulation and control method is simple and feasible.

Description

Water-assisted two-dimensional non-layered In 2 S 3 Method of growing
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a water-assisted two-dimensional materialNon-layered In 2 S 3 The method of (4).
Background
In recent years, with great attention paid to two-dimensional layered materials such as graphene and transition metal sulfides and breakthrough progress, two-dimensional non-layered materials have become one of the hot areas of research.
Two-dimensional non-laminar structures, which are chemically bonded in all three dimensions, are receiving increasing attention relative to the laminar structure of conventional two-dimensional materials. Two-dimensional materials with layered structures only occupy one corner of an iceberg in the two-dimensional materials, most of the two-dimensional materials have non-layered structures, and meanwhile, many non-layered two-dimensional materials have special properties such as magnetism, ferroelectricity and piezoelectricity, and are gradually the hot spots of research. Two-dimensional materials that are not layered structures often exhibit a specific three-dimensional morphology due to the presence of internal isotropic chemical bonds to maintain stability. When the thickness is reduced to a single atom or a few atomic layers, a large number of dangling bonds are generated on the surface, hindering the formation of a two-dimensional structure.
At present, a chemical vapor deposition technology is adopted to obtain two-dimensional nanosheets with good single-crystal property, few defects and low thickness, but the conventional chemical vapor deposition method has strict requirements on lattice matching between a growing material and a substrate, and the two-dimensional nanosheets can be grown only on Van der Waals substrates (such as fluorine crystal mica substrates) with high lattice matching degree or without dangling bonds on the surfaces, which causes great difficulty in obtaining two-dimensional non-layered materials.
Indium sulfide is a typical non-layered semiconductor that can form three different crystal structures at different temperatures: respectively alpha-phase indium sulfide (alpha-In) 2 S 3 Defect cubic), beta-phase indium sulfide (beta-In) 2 S 3 Defect spinel) and gamma-phase indium sulfide (gamma-In) 2 S 3 A layered structure). Wherein the beta-phase indium sulfide exists stably at room temperature and has a direct band gap of 1.8-2.2 eV.
The Physical Vapor Deposition (PVD) growth of the two-dimensional material has no lattice matching requirement between the preparation material and the substrate, the operation is simple, and the growth is simpleThe two-dimensional film material has large size, is compact and uniform, and can obtain a target material product with high quality and high purity because the chemical change does not occur in the material preparation process. In order to ensure high purity of the product, before the PVD growth, the deposition pipeline needs to be cleaned by high-flow inert gas such as argon to exhaust impurity gases such as air, water vapor and the like in the deposition pipeline, so as to ensure the purity of the PVD growth atmosphere. Currently, physical vapor deposition is used to prepare non-layered two-dimensional In 2 S 3 There have been some advances, but many problems still remain. Two-dimensional In 2 S 3 The physical vapor phase growth method has the main problems that the nucleation number is more in the deposition process, and the nucleation number of the indium sulfide in unit area is 10 5 -10 6 cm -2 A range that results in a smaller lateral dimension of each indium sulfide single crystal nanosheet; when the nano-crystal sheet grows on a van der Waals substrate (such as mica), the nano-crystal sheets are easily connected with each other, and a polycrystalline thin film with high grain boundary density is formed. The core of solving this problem lies In how to effectively reduce In 2 S 3 Nucleation density on a substrate, control of two-dimensional In 2 S 3 The growth uniformity of the silicon nitride film is improved, so that the film quality of the silicon nitride film is improved.
Disclosure of Invention
The invention provides a water-assisted method for preparing non-laminar two-dimensional In on mica to overcome the defects and shortcomings In the background technology 2 S 3 The method of (1) effectively reduces In the deposition process by a simple means 2 S 3 The nucleation density on the substrate, the obtained sample has good single crystal property, large size and high film quality.
To solve the above technical problems, the present invention provides, in a first aspect, a water-assisted, non-lamellar, two-dimensional In 2 S 3 The preparation method comprises the following steps:
(1) Putting an indium sulfide source into a constant temperature area at the center of a quartz tube, adding a gas washing bottle filled with deionized water into a gas path at the front end of the quartz tube, and putting a fluorine crystal mica substrate at the position which is 13-15cm away from the center of the quartz tube at the downstream of the quartz tube;
(2) Evacuating air in the quartz tube by using inert gas;
(3) Heating the constant temperature region at the center of the quartz tube to 800-850 ℃, introducing inert gas through a deionized water gas washing bottle, preserving the temperature for 10-15 minutes, and cooling to obtain non-laminar two-dimensional In on the fluorophlogopite substrate 2 S 3 . By controlling the deposition temperature and the carrier gas flow, in can be effectively reduced 2 S 3 The nucleation density on the mica substrate can obtain two-dimensional In with large transverse dimension, good single crystal property and uniform thickness 2 S 3 Nanosheets and continuous films.
Preferably, the fluorine crystal mica substrate is arranged at the downstream of the center of the quartz tube, and the temperature of the area of the fluorine crystal mica substrate is 550-650 ℃.
As a preferable scheme, the gas washing bottle filled with deionized water contains 50-100ml of deionized water.
Preferably, in the step (2), the inert gas is argon, and the flow rate of argon is 200sccm.
Preferably, in the step (3), the inert gas is argon, and the flow rate of the argon is 20 to 60sccm.
Preferably, the indium sulfide source is In 2 S 3 The powder is contained by a porcelain boat, and the mass is 50-100mg.
As a preferred embodiment, a non-lamellar two-dimensional In is prepared 2 S 3 In is hexagonal or triangular 2 S 3 Nanoplatelets having a thickness of 5-10nm and a dimension in at least one direction of 20-150 μm.
In a second aspect, the present invention provides a non-layered two-dimensional In 2 S 3 Said non-lamellar two-dimensional In 2 S 3 Non-lamellar two-dimensional In assisted by the aforementioned Water 2 S 3 The preparation method.
Preferably, the non-lamellar two-dimensional In 2 S 3 Is a single crystal nano-sheet.
Compared with the prior art, the invention has the improvement points to the prior art that: preparation of non-laminar two-dimensional In by physical vapor deposition by adding water vapor into carrier gas 2 S 3 Procedure for nanosheetAuxiliary control is carried out, water vapor does not participate In the reaction In the PVD process, the nucleation density of indium sulfide on the substrate can be effectively reduced, and the simple method can prepare independent In with large area and thin thickness 2 S 3 Nanosheets. The method has simple operation, good repeatability and high yield.
Drawings
FIG. 1 is a schematic view of a physical vapor deposition apparatus used in example 1 of the present invention;
FIG. 2 shows In obtained In example 1 2 S 3 An optical microscope image of (a);
FIG. 3 shows In obtained In example 1 2 S 3 X-ray diffraction patterns of (a);
FIG. 4 shows In obtained In example 1 2 S 3 (ii) a raman spectrogram of (a);
FIG. 5 shows In obtained In comparative example 1 2 S 3 An optical microscope image of (a);
FIG. 6 shows In obtained In comparative example 2 2 S 3 An optical microscope image of (a);
FIG. 7 is a schematic structural view of a physical vapor deposition apparatus without a DI water bottle used in comparative example 3;
FIG. 8 shows In obtained In comparative example 3 2 S 3 An optical microscope image of (a);
illustration of the drawings:
1. a deionized water bottle; 2. a heating device; 3. a quartz tube; 4. in 2 S 3 Powder; 5. a fluorine crystal mica substrate; 2', a heating device; 3', a quartz tube; 4' In 2 S 3 Powder; 5' fluorine crystal mica substrate.
Detailed Description
The present invention will be further described below by way of examples, but the present invention is not limited to the following.
Water assisted non-lamellar two-dimensional In 2 S 3 Preparation method of (2)
A first aspect of the present invention provides a water-assisted non-lamellar two-dimensional In 2 S 3 By physical vapor deposition as shown in FIG. 1The device comprises a deionized water bottle 1 and a heating device 2, in is sequentially placed In a quartz tube 3 along the direction of air inlet flow 2 S 3 Porcelain boat of powder 4 and fluorine crystal mica substrate 5. The center of the quartz tube is positioned In a constant temperature area of a heating device, the heating device can uniformly heat the constant temperature area and is filled with In 2 S 3 The porcelain boat of powder is placed in a constant temperature zone. The temperature at the two ends of the quartz tube is lower relative to the center, and the fluorine crystal mica substrate is arranged at the downstream and relatively lower temperature area (the upper and the lower parts are divided by the direction of the carrier gas flow) relative to the center. The two ends of the quartz tube are provided with air holes, wherein a gas washing bottle filled with deionized water is arranged between the front end of the air inlet and the carrier gas inlet device, and the carrier gas enters the air inlet of the quartz tube by carrying water vapor through the deionized water bottle.
Heating the central constant temperature region of the quartz tube by using a heating device to ensure that In is 2 S 3 The powder reaches the deposition temperature range, the distance between the substrate and the central constant temperature area is controlled, and In is deposited on the fluorine crystal mica substrate by utilizing the attenuation of the temperature along with the distance 2 S 3 The two-dimensional material, the fluorine crystal mica substrate in the scheme is placed at the downstream of the quartz tube and at a position 13-15cm away from the center of the quartz tube.
The method specifically comprises the following steps:
(1) Putting an indium sulfide source into a constant temperature area at the center of a quartz tube, adding a gas washing bottle filled with deionized water into a gas path at the front end of the quartz tube, and putting a fluorine crystal mica substrate into the downstream of the quartz tube along the airflow direction and at a position 13-15cm away from the center of the quartz tube; the indium sulfide source being In 2 S 3 The powder is contained by a porcelain boat, and the mass is 50-100mg.
The preferred fluorine mica substrate is placed downstream of the quartz tube in the direction of gas flow and the distance from the center of the quartz tube is selected to be 13cm,13.5cm,14cm,14.5cm,15cm.
(2) Evacuating air in the quartz tube by using inert gas, wherein the inert gas is argon, and the flow of the argon is 200sccm;
(3) Heating the constant temperature region at the center of the quartz tube to 800-850 ℃, introducing inert gas through a deionized water bottle, preserving the temperature for 10-15 minutes, cooling, and growing non-laminar two-dimensional In on the fluorine crystal mica substrate 2 S 3 . Fluorine crystal cloudThe temperature at the mother substrate placing position was 550 to 650 ℃.
The preferred heating temperature for the constant temperature zone at the center of the quartz tube may be selected from 800 deg.C, 805 deg.C, 810 deg.C, 815 deg.C, 820 deg.C, 825 deg.C, 830 deg.C, 835 deg.C, 840 deg.C, 845 deg.C, 850 deg.C.
The temperature at the position where the preferred fluorophlogopite substrate is placed can be selected to be 20 ℃,25 ℃,560 ℃,565 ℃,570 ℃,575 ℃,580 ℃,585 ℃,590 ℃,595 ℃,600 ℃,605 ℃,610 ℃,615 ℃,620 ℃,625 ℃,630 ℃,635 ℃,640 ℃,645 ℃ and 650 ℃.
The inert gas in the step (3) is argon, the flow rate of the argon is 20-60sccm, if the flow rate of the argon is lower than the lower limit of the preferred range, the water vapor content in the argon is reduced, nano sheets with regular shapes and independence are difficult to appear on the surface of a mica substrate sample, the nano sheets are mutually connected, and the sample presents the appearance of a film; if the argon flow rate is higher than the upper limit of the preferred range, in is on the surface of the mica substrate 2 S 3 It is difficult to nucleate efficiently and the sample amount decreases.
A preferred flow rate of argon gas may be selected from the group consisting of 20sccm,25sccm,30sccm,35sccm,40sccm,45sccm,50sccm,55sccm, and 60sccm.
And controlling the tubular furnace to keep the temperature for 10-15 minutes at the growth temperature, and if the temperature is lower than the lower limit of the preferred range, depositing In on the mica substrate 2 S 3 The nano-sheet has small size; in if the holding time is higher than the upper limit of the preferred range 2 S 3 Stacking growth is carried out, the nucleation number is increased, and the nano sheets are connected with each other to form a continuous film with small grain boundary density.
Preferred incubation times may be selected from 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes.
By controlling the deposition temperature and the carrier gas flow, in can be effectively reduced 2 S 3 The nucleation density on the mica substrate can obtain two-dimensional In with large transverse dimension, good single crystal property and uniform thickness 2 S 3 Nanosheets and continuous films. Prepared non-lamellar two-dimensional In 2 S 3 In is hexagonal or triangular 2 S 3 Nano-meterA sheet having a thickness of 5-10nm and a dimension in at least one direction of 20-150 μm.
Non-lamellar two-dimensional In 2 S 3
In a second aspect, the present invention provides a non-layered two-dimensional In 2 S 3 Said non-lamellar two-dimensional In 2 S 3 Non-lamellar two-dimensional In assisted by the aforementioned Water 2 S 3 The preparation method.
Preferably, the non-lamellar two-dimensional In 2 S 3 Is a single crystal nano-sheet.
The inner diameter of the quartz tube used in example 1 of the present invention and comparative examples 1 to 3 was 21mm. The specific process comprises the following steps: introducing large-flow argon for 15 minutes to exhaust air in the quartz tube, adjusting the argon passing through the deionized water gas washing bottle to be in a flow selected range when the temperature is raised, and naturally cooling to room temperature after the temperature is kept.
Example 1
50mg of In were weighed 2 S 3 Putting the powder into a porcelain boat, placing the porcelain boat in a temperature zone of 825 ℃, placing the fluorine crystal mica substrate in the porcelain boat, and placing the fluorine crystal mica substrate in a temperature zone of 600 ℃. Substrate and In 2 S 3 The distance of the source was controlled at 13cm. Before the temperature rise is started, argon gas with the flow rate of 200sccm is introduced into the quartz tube, and the air in the quartz tube is exhausted. Argon gas with the flow of 40sccm flows into the quartz tube through the deionized water bottle when the temperature rise is started, the heating device is heated to 825 ℃ at the heating rate of 40 ℃/min, and the temperature is kept for 12 minutes. After the heat preservation is finished, naturally cooling to room temperature, and closing the air flow to obtain the two-dimensional In 2 S 3 Nanoplatelets having a nucleation density of about 1.2 x 10 4 cm -2 The thickness is 5nm, and the transverse size of the nano-sheet is 20-60 mu m.
FIG. 1 is a schematic view of the physical vapor deposition apparatus used in example 1;
FIG. 2 shows In obtained In example 1 2 S 3 An optical microscope image of (a);
FIG. 3 shows In obtained In example 1 2 S 3 X-ray diffraction patterns of (a);
FIG. 4 shows In obtained In example 1 2 S 3 Raman spectrum of；
Comparative example 1
The difference compared to example 1 is that the argon carrier gas flow during the incubation was 15sccm.
50mg of In were weighed 2 S 3 Putting the powder into a porcelain boat, placing the porcelain boat in a temperature zone of 825 ℃, placing the fluorine crystal mica substrate in the porcelain boat, and placing the fluorine crystal mica substrate in a temperature zone of 600 ℃. Substrate and In 2 S 3 The distance of the source was controlled at 13cm. Before the temperature rise is started, argon gas with the flow rate of 200sccm is introduced into the quartz tube, and the air in the quartz tube is exhausted. When the temperature rise starts, argon gas with the flow of 15sccm is introduced into the quartz tube through the deionized water bottle, the temperature of the heating device is raised to 825 ℃ at the heating rate of 40 ℃/min, and the temperature is kept for 12 minutes. After the heat preservation is finished, naturally cooling to room temperature, and closing the air flow to obtain the two-dimensional In 2 S 3 Nanoplatelets having a nucleation density of about 3 x 10 5 cm -2 And the transverse size of the nano sheet is 5-10 mu m.
FIG. 5 shows In obtained In comparative example 1 2 S 3 An optical microscope image of (a);
comparative example 2
The difference compared to example 1 is that the incubation time was 20 minutes.
50mg of In were weighed 2 S 3 Putting the powder into a porcelain boat, placing the porcelain boat in a temperature zone of 825 ℃, placing the fluorine crystal mica substrate in the porcelain boat, and placing the fluorine crystal mica substrate in a temperature zone of 600 ℃. Substrate and In 2 S 3 The distance of the source was controlled at 13cm. Before the temperature rise is started, argon gas with the flow rate of 200sccm is introduced into the quartz tube, and the air in the quartz tube is exhausted. When the temperature rise starts, argon gas with the flow of 40sccm is introduced into the quartz tube through the deionized water bottle, the temperature of the heating device is raised to 825 ℃ at the heating rate of 40 ℃/min, and the temperature is kept for 20 minutes. After the heat preservation is finished, naturally cooling to room temperature, and closing the air flow to obtain mutually connected two-dimensional In 2 S 3 Nanoplatelets having a nucleation density of about 1.6 x 10 5 cm -2 And the transverse size of the nano sheet is 5-20 mu m.
FIG. 6 shows In obtained In comparative example 2 2 S 3 Optical microscopy of (a).
Comparative example 3
Compared with the embodiment 1, the difference is that in the physical vapor deposition process, the argon carrier gas is directly introduced into the quartz tube without passing through the deionized water bottle.
50mg of In were weighed 2 S 3 Putting the powder into a porcelain boat, placing the porcelain boat in a temperature zone of 825 ℃, placing the fluorine crystal mica substrate in the porcelain boat, and placing the fluorine crystal mica substrate in a temperature zone of 600 ℃. Substrate and In 2 S 3 The distance of the source was controlled at 13cm. Before the temperature rise is started, argon gas with the flow rate of 200sccm is introduced into the quartz tube, and the air in the quartz tube is exhausted. Argon gas with the flow of 40sccm is introduced into the quartz tube when the temperature rise is started, the heating device is heated to 825 ℃ at the heating rate of 40 ℃/min, and the temperature is kept for 12 minutes. After the heat preservation is finished, naturally cooling to room temperature, and closing the air flow to obtain the two-dimensional In 2 S 3 Nanoplatelets having a nucleation density of about 1.2 x 10 6 cm -2 And the transverse size of the nano sheet is 0.5-4 mu m.
FIG. 7 is a schematic view showing the structure of a physical vapor deposition apparatus without a deionized water bottle used in comparative example 3;
FIG. 8 shows In obtained In comparative example 3 2 S 3 An optical microscope image of (a);
by comparing the documents example 1 and comparative example 3, it can be seen that the water-assisted preparation of non-lamellar two-dimensional In is used 2 S 3 When the nano-sheet is prepared, because the deionized water gas washing bottle can introduce a small amount of water vapor into argon carrier gas, the water vapor is supposed to inhibit In the physical vapor deposition process 2 S 3 So that the difference in nucleation density with or without steam assistance is 1.2X 10 4 cm -2 And 1.2X 10 6 cm -2 By such a difference of two orders of magnitude, water is not generally introduced In physical vapor deposition, while the applicants have creatively introduced water vapor, which greatly reduces In 2 S 3 The nucleation density of the crystal is larger than that of the conventional physical vapor deposition, and larger In can be grown In the further growth process 2 S 3 Single crystal plate, in thus grown on a fluorine crystal mica substrate 2 S 3 The grain boundary of the single crystal wafer is greatly reduced, and In is greatly facilitated 2 S 3 Application in semiconductor devices.
By comparing example 1 withIn the proportion of 1, it was found that the flow of the carrier gas was too small, the amount of the introduced water vapor was too small, and In was not influenced appropriately at all 2 S 3 The applicant has repeatedly tested that the flow rate of the carrier gas in step (3) is 20-60sccm, preferably argon, and can be selected from 20sccm,25sccm,30sccm,35sccm,40sccm,45sccm,50sccm,55sccm and 60sccm.
By comparing example 1 with comparative example 2, comparative example 2 shows that the nucleation density is more than an order of magnitude worse due to the excessively long holding time and In 2 S 3 Stacking growth is carried out, the nucleation number is increased, and the nano sheets are connected with each other to form a continuous film with small grain boundary density. The applicant has found that the incubation time in step (3) is 10-15 minutes through repeated experiments, and the preferred incubation time can be selected from 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes and 15 minutes.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (9)

1. Water-assisted two-dimensional non-layered In 2 S 3 The method for growing, characterized by comprising the steps of:
(1) Putting an indium sulfide source into a constant temperature area at the center of a quartz tube, adding a gas washing bottle filled with deionized water into a gas path at the front end of the quartz tube, and putting a fluorine crystal mica substrate into the downstream of the quartz tube and at a position 13-15cm away from the center of the quartz tube;
(2) Evacuating air in the quartz tube by using inert gas;
(3) Heating the constant temperature region at the center of the quartz tube to 800-850 ℃, introducing inert gas through a deionized water gas washing bottle, preserving the temperature for 10-15 minutes, and cooling to obtain the fluorine crystal mica substrateObtaining non-lamellar two-dimensional In 2 S 3 。
2. The production method according to claim 1, wherein the fluorine crystal mica substrate is placed downstream of the center of the quartz tube and the temperature of the area of the fluorine crystal mica substrate is 550 to 650 ℃.
3. The method of claim 1, wherein the gas washing bottle containing deionized water contains 50 to 100ml of deionized water.
4. The method according to claim 1, wherein in the step (2), the inert gas is argon gas, and a flow rate of the argon gas is 200sccm.
5. The method according to claim 1, wherein in the step (3), the inert gas is argon gas, and a flow rate of the argon gas is 20 to 60sccm.
6. The method of any of claims 1-5, wherein the indium sulfide source is In 2 S 3 The powder is contained by a porcelain boat, and the mass is 50-100mg.
7. The method of any of claims 1-5, wherein the non-layered, two-dimensional In is prepared 2 S 3 In is hexagonal or triangular 2 S 3 Nanoplatelets having a thickness of 5-10nm and a dimension in at least one direction of 20-150 μm.
8. Non-laminated two-dimensional In 2 S 3 Characterized In that the non-lamellar two-dimensional In 2 S 3 Use of the water-assisted, non-lamellar, two-dimensional In of any of claims 1 to 7 2 S 3 The method of (2).
9. The non-layered, two-dimensional In of claim 8 2 S 3 Which is characterized in thatSaid non-lamellar two-dimensional In 2 S 3 Is a single crystal nano-sheet.
CN202210994862.5A 2022-08-18 2022-08-18 Water-assisted two-dimensional non-lamellar In 2 S 3 Growth method of (2) Active CN115323482B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210994862.5A CN115323482B (en) 2022-08-18 2022-08-18 Water-assisted two-dimensional non-lamellar In 2 S 3 Growth method of (2)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210994862.5A CN115323482B (en) 2022-08-18 2022-08-18 Water-assisted two-dimensional non-lamellar In 2 S 3 Growth method of (2)

Publications (2)

Publication Number Publication Date
CN115323482A true CN115323482A (en) 2022-11-11
CN115323482B CN115323482B (en) 2023-08-04

Family

ID=83926291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210994862.5A Active CN115323482B (en) 2022-08-18 2022-08-18 Water-assisted two-dimensional non-lamellar In 2 S 3 Growth method of (2)

Country Status (1)

Country Link
CN (1) CN115323482B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108531981A (en) * 2018-03-09 2018-09-14 广东工业大学 A method of preparing two-dimentional indium trisulfide monocrystalline in mica substrate
CN110473925A (en) * 2019-07-09 2019-11-19 广东工业大学 A kind of two dimension molybdenum sulfide/indium sulfide transverse direction hetero-junctions and its preparation method and application
CN110846719A (en) * 2019-11-28 2020-02-28 华中科技大学 Two-dimensional non-layered In2SnS4Crystalline material and method for producing same
CN112663144A (en) * 2020-12-10 2021-04-16 华中科技大学 Two-dimensional In2S3Preparation method of/SnS heterojunction crystalline material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108531981A (en) * 2018-03-09 2018-09-14 广东工业大学 A method of preparing two-dimentional indium trisulfide monocrystalline in mica substrate
CN110473925A (en) * 2019-07-09 2019-11-19 广东工业大学 A kind of two dimension molybdenum sulfide/indium sulfide transverse direction hetero-junctions and its preparation method and application
CN110846719A (en) * 2019-11-28 2020-02-28 华中科技大学 Two-dimensional non-layered In2SnS4Crystalline material and method for producing same
CN112663144A (en) * 2020-12-10 2021-04-16 华中科技大学 Two-dimensional In2S3Preparation method of/SnS heterojunction crystalline material

Also Published As

Publication number Publication date
CN115323482B (en) 2023-08-04

Similar Documents

Publication Publication Date Title
CN104389016B (en) Method for quickly preparing large-size single-crystal graphene
JP5563500B2 (en) Synthesis method of graphene and carbon molecular thin film
CN110257906B (en) Two-dimensional transition metal chalcogenide crystal and preparation method and application thereof
CN112941627B (en) Ultrathin Cr growing vertically 2 Te 3 Preparation method of monocrystal nanosheets
Cao et al. Influences of carrier gas flow rate on the morphologies of MoS2 flakes
CN106335897B (en) A kind of large single crystal bilayer graphene and preparation method thereof
CN113550006B (en) Method for preparing two-dimensional tellurium single crystal on mica substrate
CN102409399A (en) Method for preparing high-quality graphene
Wang et al. Synthesis of large-area graphene films on rolled-up Cu foils by a “breathing” method
CN113666418A (en) Two-dimensional atomic crystal multilayer corner WS2Nano material and preparation method thereof
CN110616414A (en) Method for preparing two-dimensional BiOBr film
CN112456452B (en) Preparation method of germanium diselenide nano material
GB2615867A (en) A method of forming a graphene layer structure and a graphene substrate
CN115341273B (en) Preparation of large-size two-dimensional thermoelectric material bismuth telluride single crystal
CN115323482B (en) Water-assisted two-dimensional non-lamellar In 2 S 3 Growth method of (2)
GB2605211A (en) A method of forming a graphene layer structure and a graphene substrate
CN111074234A (en) Device and method for growing two-dimensional material based on push-pull trolley mode
Tucic et al. Pyrosol preparation and structural characterization of SnO2 thin films
CN115341272B (en) Preparation method of millimeter-level two-dimensional topological material bismuth selenide monocrystal
Gusev et al. Research of morphology and structure of 3C–SiC thin films on silicon by electron microscopy and X-ray diffractometry
CN113981542B (en) Method for preparing high-quality single-crystal-domain two-dimensional material by regulating and controlling cavity pressure
CN114752917B (en) Method for preparing two-dimensional magnetic material chromium-based chalcogenide and heterojunction thereof
CN116497444B (en) Realizing large-area two-dimensional lamellar material In 2 Se 3 Chemical vapor deposition growth method of (2)
KR101210958B1 (en) Fabrication Method of Ferromagnetic Single Crystal
CN109399621B (en) Method for preparing large-area high-quality graphene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant