CN114540956A - Preparation method of niobium-doped two-dimensional tungsten sulfide crystal material - Google Patents
Preparation method of niobium-doped two-dimensional tungsten sulfide crystal material Download PDFInfo
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- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000013078 crystal Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 44
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 43
- 239000010937 tungsten Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 35
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011888 foil Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000010955 niobium Substances 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims description 51
- 229910052717 sulfur Inorganic materials 0.000 claims description 33
- 239000011593 sulfur Substances 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 abstract description 32
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 12
- 230000005669 field effect Effects 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000011010 flushing procedure Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020042 NbS2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- -1 Transition Metal Disulfides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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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
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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
- 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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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of niobium-doped two-dimensional tungsten sulfide crystal material, which adopts a chemical vapor deposition method and adopts Si/SiO2The niobium-doped two-dimensional tungsten sulfide crystal material is prepared on a substrate, wherein a metal tungsten foil is a tungsten source, a metal niobium foil is a niobium source, the growth substrate is reversely buckled on the metal tungsten foil, the area of the metal niobium foil is smaller than that of the metal tungsten foil, one end of the growth substrate is directly contacted with the metal tungsten foil, the other end of the growth substrate is arranged right above the niobium source and reacts with sulfur vapor. The obtained single-layer niobium-doped tungsten sulfide crystal material can be used as a channel material of a transistor and applied to the field of ultrathin high-efficiency field effect transistors.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a niobium-doped two-dimensional tungsten sulfide crystal material.
Background
Since the discovery of graphene, ultra-thin two-dimensional semiconductor materials with excellent optical, electrical and thermal properties, such as Transition Metal Disulfides (TMDs), black phosphorus, Boron Nitride (BN), etc., have attracted attention and have promising application potential in the fields of field effect transistors, photodetectors, light emitting diodes, energy sources, etc. Compared with the bulk material, the tungsten disulfide (WS)2) The representative two-dimensional TMDs have indirect-direct band gap transition related to layer number, adjustable bandwidth, high light emission efficiency, and high yieldRich excitons, good flexibility, and the like. At present, the research on the growth of various single-layer TMDs crystals with different morphologies and two-dimensional TMDs crystals with different morphologies and layers by using chemical vapor deposition, pulse laser deposition, metal organic chemical vapor deposition and other methods is helpful for defining the growth process and establishing the inherent growth mechanism of the two-dimensional TMDs crystals, thereby greatly promoting the controllable growth of the two-dimensional atomic crystals. The controllable growth of the high-quality two-dimensional TMDS atomic crystal is expected to accelerate the application of the high-quality two-dimensional TMDS atomic crystal in the field of high-performance and low-energy-consumption ultrathin optoelectronic devices.
WS2The crystal can show excellent physical characteristics, such as from a block body to a single layer, not only can be converted from an indirect band gap to a direct band gap, but also has physical properties of a wider layer number adjustable band gap (1.3-2.1 electron volts), stronger light-substance interaction, spin valley coupling phenomenon and the like. In addition, WS2Has stronger fluorescence emission in visible light and near infrared spectrum regions. At the same time, based on WS2The constructed transistor has high on/off ratio (-10)7) The carrier mobility can reach 214cm2V-1s-1. However, single-layer WS2The electrical properties of the crystal are yet to be further improved. Although Mo is constructed by doping or alloying1-xWxS2，WS2xSe2(1-x),WTe2xS2(1-x)It can be seen that doped or alloyed ternary WS is obtained by substitution based on elements of the same family having the same outermost electrons2Based on two-dimensional crystals, whereby it is difficult to change WS2Carrier type and density, which makes it difficult to achieve WS2Modulation of optical and electrical properties. At present, chemical vapor deposition has proven to produce high quality thin layers WS2The most effective method of crystal is based on the regulation and control of experimental parameters, and has synthesized a plurality of monolayer WS with different morphologies2And (4) crystals.
However, niobium (Nb) doping of two-dimensional WS using one-step chemical vapor deposition2The controlled growth of crystalline materials remains to be studied further. Nb doped single layer WS2The crystal can not only realize halfThe transition from conductor to metal has higher carrier density and can modulate the single layer WS2Luminescent properties of the crystals. Therefore, a simple and feasible way for realizing the preparation of the Nb-doped two-dimensional tungsten sulfide crystal material is yet to be developed, and the photoelectric properties of the Nb-doped two-dimensional tungsten sulfide crystal material are expected to be further optimized and researched, so that the application of the Nb-doped two-dimensional tungsten sulfide crystal material in the fields of field effect transistors, photodetectors, photonic devices and the like is met.
Disclosure of Invention
The invention aims to provide a preparation method of a niobium-doped two-dimensional tungsten sulfide crystal material, which realizes the preparation of the niobium-doped two-dimensional tungsten sulfide crystal material by a chemical vapor deposition method, thereby realizing the growth of the niobium-doped two-dimensional tungsten sulfide crystal material by a one-step method; meanwhile, the method has the advantages of simple operation process, low cost, no catalyst and environmental friendliness.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a niobium-doped two-dimensional tungsten sulfide crystal material comprises the following steps:
s1 in the form of Si/SiO2For the growth substrate, the metal niobium foil is a niobium source, the metal tungsten foil is a tungsten source, and the sulfur powder is a sulfur source;
s2, sequentially setting a sulfur source temperature area and a deposition temperature area in a double-temperature-area horizontal tube furnace according to the airflow direction, placing two quartz boats in the same quartz tube, placing the quartz tube in the tube furnace, placing a sulfur source on one quartz boat, locating the sulfur source temperature area, placing a niobium source, a tungsten source and a growth substrate on the other quartz boat, flatly laying a metal niobium foil on the surface of one end of the metal tungsten foil, enabling the end to be close to the sulfur source temperature area, enabling the area of the metal niobium foil to be smaller than that of the metal tungsten foil, reversely buckling the substrate right above the metal tungsten foil, supporting one end of the substrate, close to the sulfur source temperature area, by using a quartz column, enabling the other end to be in contact with the metal tungsten foil, and enabling the quartz boats to be located in the deposition temperature area;
s3, vacuumizing the quartz tube, introducing inert gas into the quartz tube, heating the sulfur source temperature region and the deposition temperature region, wherein the target temperature of the sulfur source temperature region is 260-280 ℃, the target temperature of the deposition temperature region is 890-910 ℃, and the two temperature regions are simultaneously heated to the set target temperature value;
s4, conveying sulfur vapor to a deposition temperature area by inert gas to react with tungsten for 15-25 minutes to obtain a niobium-doped two-dimensional tungsten sulfide crystal material on the substrate, and cooling to room temperature under the protection of the inert gas after the reaction is finished.
Preferably, Si/SiO2The growth substrate is a silicon wafer without a catalyst and a seed layer, and the size of the growth substrate is 1cm multiplied by 3 cm.
Preferably, the mass purity of the metal niobium foil is 99.99%, the size of the metal niobium foil is 0.5cm multiplied by 0.5cm, the mass purity of the metal tungsten foil is 99.99%, the size of the metal tungsten foil is 1cm multiplied by 3cm, the mass purity of the sulfur powder is 99.99%, and the adding amount is 300-400 mg.
Preferably, the sulfur source quartz boat is close to the gas inlet end of the tube furnace.
Preferably, the quartz column is vertically supported, the bottom of the quartz column is in contact with the metal tungsten foil, and the height of the quartz column is 0.5-0.9 mm.
Preferably, the distance between the two quartz boats is 16-18 cm.
Preferably, the inert gas is argon.
Preferably, in S3, after the quartz tube is evacuated, the quartz tube is purged with 500 cc/min argon gas for 10 minutes.
Preferably, in S4, the operation of simultaneously raising the temperature of the two temperature zones to the set target temperature value is as follows: the deposition temperature zone is heated to 590-610 ℃ at a heating rate of 26 ℃/min, and then the sulfur source temperature zone is heated.
Preferably, the argon introducing speed in the temperature rising stage and the reaction stage of the two temperature zones is 80-120 cubic centimeters per minute.
The invention has the beneficial effects that:
1. the preparation of the niobium-doped two-dimensional tungsten sulfide crystal material is realized by a one-step chemical vapor deposition method, which is probably because the niobium element can effectively partially replace the tungsten element at high temperature, so that the niobium-doped two-dimensional single-layer tungsten sulfide crystal can be realized.
2. The method has the advantages of simple operation, low cost, no catalyst and environmental protection.
3. The preparation of the niobium-doped two-dimensional tungsten sulfide crystal material is beneficial to modulating the optical and electrical properties of tungsten sulfide, thereby realizing the application in the field of high-efficiency optoelectronic devices.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a single-layer two-dimensional tungsten sulfide triangular plate according to an embodiment of the present invention.
FIG. 2 is an optical photograph of a single-layer two-dimensional tungsten sulfide triangular plate made according to an embodiment of the present invention.
Fig. 3 is a raman spectrum of the single-layer two-dimensional tungsten sulfide triangular plate manufactured in the embodiment of the present invention.
FIG. 4 is a photoluminescence spectrum of a single-layer two-dimensional tungsten sulfide triangular plate made according to an embodiment of the invention.
FIG. 5 is a schematic diagram of an apparatus for preparing a niobium-doped single-layer two-dimensional tungsten sulfide triangular plate according to the second embodiment of the present invention.
FIG. 6 is a photo of a niobium doped monolayer two-dimensional tungsten sulfide delta prepared in example two.
FIG. 7 is a Raman spectrum of a niobium-doped single-layer two-dimensional tungsten sulfide triangular plate prepared in example II of the present invention.
FIG. 8 is a photoluminescence spectrum of a niobium-doped single-layer two-dimensional tungsten sulfide triangular plate prepared in the second embodiment of the invention.
Detailed Description
The present invention will be further described with reference to the structures or terms used herein. The description is given for the sake of example only, to illustrate how the invention may be implemented, and does not constitute any limitation on the invention.
EXAMPLES preparation of a two-dimensional monolayer tungsten sulfide delta
A two-dimensional single-layer tungsten sulfide triangular plate is prepared by chemical vapor deposition with Si/SiO2The deposition substrate is prepared by reacting tungsten (W) as a tungsten source with sulfur source sulfur powder (S). The preparation is carried out in a double-temperature-zone horizontal tube furnace, the schematic diagram of the device is shown in figure 1, and the preparation method specifically comprises the following preparation steps:
s1, selecting Si/SiO without catalyst and seed layer2A substrate, the size of the substrate is 1cm multiplied by 3 cm;
s2, sequentially setting a sulfur source temperature area and a deposition temperature area in the double-temperature-area horizontal tube furnace according to the airflow direction; placing quartz boats filled with 30 mg of S powder in a sulfur source temperature area, reversely buckling a substrate right above a metal tungsten foil, vertically supporting one end of the substrate close to a sulfur source by using a quartz column, contacting the other end of the substrate with the metal tungsten foil, directly contacting the bottom of the quartz column with the metal tungsten foil, placing the quartz columns with the height of about 0.9 mm in a deposition temperature area, placing the two quartz boats in the same quartz tube, and placing the quartz tube in a tube furnace;
s3, vacuumizing the quartz tube before heating, and flushing with 500 cubic centimeters per minute (99.99%) of high-purity argon for 10 minutes to remove residual oxygen and moisture in the quartz tube; heating the deposition area to 590 ℃ at a heating rate of 26 ℃/min under the protection of high-purity Ar gas of 90 cubic centimeters per minute, wherein the sulfur source temperature area starts to be heated, the target temperature of the sulfur source temperature area is 270 ℃, the target temperature of the deposition temperature area is 890 ℃, and the two temperature areas are heated to a set target temperature value simultaneously;
and (3) conveying the S4 vapor to a deposition temperature area by argon gas to react with tungsten for 15 minutes to obtain a large-range two-dimensional single-layer tungsten sulfide triangular plate on the substrate, and cooling to room temperature under the protection of argon gas after the reaction is finished.
FIG. 2 is a high magnification photomicrograph of a high density two-dimensional monolayer tungsten sulfide trigone, showing that the individual crystal shapes are substantially triangular in shape and that they are all relatively uniform in color, indicating that the structure is relatively uniform in thickness with an average edge length of about 10 micrometers.
FIG. 3 shows a Raman spectrum of a triangular plate at the center position of 352.1cm-1And 418.3cm-1Can be attributed to the hexagonal phase WS22LA (M) and A1gMode (F) of only 66.2cm difference-1The thickness of the trigonal feature is shown as a monolayer, since similar differences are indicated in the reported literature as monolayer tungsten sulfide.
FIG. 4 is a diagram showing the photoluminescence spectrum of the triangular plate at the center, which has only one strong emission peak at 618 nm, and the emission peak at 618 nm is known from the reported literatureDirect exciton luminescence attributable to a monolayer of tungsten sulfide. From the luminescence spectrum, it can be known that the prepared tungsten sulfide triangular plate is single-layer. The detection result shows that the two-dimensional triangular plate prepared by the chemical vapor deposition method is a single-layer two-dimensional WS2Crystalline and hexagonal phase.
The experimental conditions of the first embodiment are to grow a single layer of tungsten sulfide, and the second embodiment introduces a niobium source on the basis of the first embodiment, so that the preparation of the niobium-doped tungsten sulfide triangular plate is realized.
EXAMPLE preparation of niobium Bib doped two-dimensional tungsten sulfide crystalline Material
A process for preparing the niobium doped two-dimensional tungsten sulfide crystal material by chemical vapor deposition method with Si/SiO2The material is prepared by reacting a substrate, a metal niobium foil, a metal tungsten foil and sulfur powder, wherein the substrate is a deposition substrate, the metal niobium foil is a niobium (Nb) source, the metal tungsten foil is a tungsten (W) source and the sulfur powder is a sulfur source. The preparation is carried out in a double-temperature-zone horizontal tube furnace, the schematic diagram of the device is shown in figure 5, and the preparation method specifically comprises the following preparation steps:
s1, selecting Si/SiO without catalyst and seed layer2And growing a substrate, wherein the size of the substrate is 1cm multiplied by 3 cm.
S2, setting a sulfur source temperature area and a deposition temperature area in sequence according to the airflow direction in a double-temperature-area horizontal tube furnace, placing two quartz boats in the same quartz tube, placing the quartz tube in the tube furnace, placing one quartz boat filled with 300 milligrams of S powder in the sulfur source temperature area, placing a niobium source, a tungsten source and a growth substrate on the other quartz boat, placing a metal niobium foil with the size of 0.5cm multiplied by 0.5cm on the surface of one end of a metal tungsten foil with the size of 1cm multiplied by 3cm, wherein the end is close to the sulfur source temperature area, reversely buckling the substrate right above the metal tungsten foil, vertically supporting one end of the substrate close to the sulfur source temperature area by a quartz column, contacting the other end of the substrate with the metal tungsten, the height of the quartz column is about 0.9 microns, contacting the bottom of the quartz column with the metal tungsten foil, placing the quartz boats in the deposition temperature area, wherein the distance between the two quartz boats is 16cm, and the mass of the metal niobium foil, the metal tungsten foil and the sulfur powder is 99.99%.
S3, flushing with 500 cubic centimeters/minute high-purity argon (99.99%) for 10 minutes before heating for removing residual oxygen and moisture in the cavity; heating the deposition temperature zone to 590 ℃ under the protection of high-purity Ar gas of 90 cubic centimeters per minute at the heating rate of 26 ℃/min, starting heating the sulfur source temperature zone, wherein the target temperature of the sulfur source temperature zone is 270 ℃, the target temperature of the deposition temperature zone is 890 ℃, and the two temperature zones are simultaneously heated to the set target temperature value;
and S4, conveying S steam to a deposition temperature area by argon gas to react with W, wherein the reaction time is 15 minutes, obtaining a large-range niobium-doped two-dimensional tungsten sulfide crystal material on the substrate, and cooling to room temperature under the protection of argon gas after the reaction is finished.
FIG. 6 is a high magnification photomicrograph of a high density niobium doped two dimensional tungsten sulfide crystal platelet showing that the individual crystal shapes are substantially triangular or butterfly shaped and that they are relatively uniform in color, indicating that the structure is relatively uniform in thickness with an average edge length of about 18 microns.
FIG. 7 shows a Raman spectrum of a triangular plate at the center position of 352.1cm-1And 416.3cm-1Can be attributed to hexagonal phase WS22LA (M) and A1gMode (Γ) of only 64.2cm difference-1Indicating that the thickness of the trigonal feature may be a monolayer, since similar differences are indicated in the reported literature as monolayer tungsten sulfide. Furthermore, it is located at 147.1cm-1And 385.2cm-1The two characteristic Raman peaks of (A) can be attributed to single-layer NbS2The I peak and the a1 peak of (a) because similar peak positions are indicated in the reported literature as single layers of niobium sulfide.
FIG. 8 is a photoluminescence spectrum of the triangular plate at the center, which has only one strong emission peak at 627 nm, and compared with the single layer of tungsten sulfide in the first embodiment, the peak position is red-shifted, the intensity is reduced, and the full width at half maximum is increased, which indicates that niobium atoms in the tungsten sulfide enter the crystal lattice to form niobium-doped tungsten sulfide. The detection result shows that the niobium-doped single-layer two-dimensional tungsten sulfide crystal material is prepared by a chemical vapor deposition method.
In summary, the invention realizes the growth of large-scale niobium-doped two-dimensional tungsten sulfide crystal material by chemical vapor deposition method and by utilizing the difference of the evaporation temperature and the sulfide growth temperature of the metal tungsten and the metal niobium.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a niobium-doped two-dimensional tungsten sulfide crystal material is characterized by comprising the following steps of:
s1 in the form of Si/SiO2For the growth substrate, the metal niobium foil is a niobium source, the metal tungsten foil is a tungsten source, and the sulfur powder is a sulfur source;
s2, sequentially setting a sulfur source temperature area and a deposition temperature area in a double-temperature-area horizontal tube furnace according to the airflow direction, placing two quartz boats in the same quartz tube, placing the quartz tube in the tube furnace, placing a sulfur source on one quartz boat, locating the sulfur source temperature area, placing a niobium source, a tungsten source and a growth substrate on the other quartz boat, flatly laying a metal niobium foil on the surface of one end of the metal tungsten foil, enabling the end to be close to the sulfur source temperature area, enabling the area of the metal niobium foil to be smaller than that of the metal tungsten foil, reversely buckling the substrate right above the metal tungsten foil, supporting one end of the substrate, close to the sulfur source temperature area, by using a quartz column, enabling the other end to be in contact with the metal tungsten foil, and enabling the quartz boats to be located in the deposition temperature area;
s3, vacuumizing the quartz tube, introducing inert gas into the quartz tube, heating the sulfur source temperature region and the deposition temperature region, wherein the target temperature of the sulfur source temperature region is 260-280 ℃, the target temperature of the deposition temperature region is 890-910 ℃, and the two temperature regions are simultaneously heated to the set target temperature value;
s4, conveying sulfur vapor to a deposition temperature area by inert gas to react with tungsten for 15-25 minutes to obtain a niobium-doped two-dimensional tungsten sulfide crystal material on the substrate, and cooling to room temperature under the protection of the inert gas after the reaction is finished.
2. The method of claim 1, wherein the Si/SiO is selected from the group consisting of2The growth substrate is a silicon wafer without a catalyst and a seed layer, and the size of the growth substrate is 1cm multiplied by 3 cm.
3. The method for preparing a niobium-doped two-dimensional tungsten sulfide crystal material as claimed in claim 1, wherein the mass purity of the metal niobium foil is 99.99%, the size is 0.5cm × 0.5cm, the mass purity of the metal tungsten foil is 99.99%, the size is 1cm × 3cm, the mass purity of the sulfur powder is 99.99%, and the addition amount is 300-400 mg.
4. The method for preparing niobium-doped two-dimensional tungsten sulfide crystal material according to claim 1, wherein the sulfur source quartz boat is close to the gas inlet end of the tube furnace.
5. The method of claim 1, wherein the quartz pillars are vertically supported and the bottoms of the quartz pillars are in contact with the tungsten foil, and the height of the quartz pillars is 0.5-0.9 mm.
6. The method of claim 1, wherein the two quartz boats are spaced apart by 16-18 cm.
7. The method of claim 1, wherein the inert gas is argon.
8. The method for preparing a niobium-doped two-dimensional tungsten sulfide crystal material as claimed in claim 7, wherein in S3, after the quartz tube is vacuumized, the quartz tube is cleaned with argon gas of 500 cc/min for 10 min.
9. The method for preparing niobium-doped two-dimensional tungsten sulfide crystal material as claimed in claim 7, wherein in S4, the operation of simultaneously raising the temperature of the two temperature zones to the set target temperature value comprises: the deposition temperature zone is heated to 610 ℃ at a heating rate of 26 ℃/min, and then the sulfur source temperature zone is heated.
10. The method of claim 7, wherein the argon is introduced at a rate of 80-120 cc/min during the heating step and the reacting step of the two temperature zones.
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