CN114709137A - WS2/MoS2 two-dimensional coherent heterojunction network material and preparation method thereof - Google Patents
WS2/MoS2 two-dimensional coherent heterojunction network material and preparation method thereof Download PDFInfo
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- 230000001427 coherent effect Effects 0.000 title claims abstract description 59
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 59
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 22
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
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- 239000010937 tungsten Substances 0.000 claims abstract description 23
- 238000004073 vulcanization Methods 0.000 claims abstract description 19
- 229910016021 MoTe2 Inorganic materials 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 64
- 229910052786 argon Inorganic materials 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 28
- 239000012159 carrier gas Substances 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical group O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 3
- 230000012010 growth Effects 0.000 abstract description 26
- 238000010438 heat treatment Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 13
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- 238000011144 upstream manufacturing Methods 0.000 description 8
- 238000000089 atomic force micrograph Methods 0.000 description 6
- HITXEXPSQXNMAN-UHFFFAOYSA-N bis(tellanylidene)molybdenum Chemical compound [Te]=[Mo]=[Te] HITXEXPSQXNMAN-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- 238000010586 diagram Methods 0.000 description 3
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- 150000002431 hydrogen Chemical class 0.000 description 3
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- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- 229910003090 WSe2 Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
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- 235000002779 Morchella esculenta Nutrition 0.000 description 1
- 240000002769 Morchella esculenta Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XCUPBHGRVHYPQC-UHFFFAOYSA-N sulfanylidenetungsten Chemical compound [W]=S XCUPBHGRVHYPQC-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a WS2/MoS2A two-dimensional coherent heterojunction network material is prepared by chemical vapor deposition of 2H-phase single crystal MoTe2Carrying out a vulcanization reaction on the layer to obtain a vulcanized product, and reacting the vulcanized product with a tungsten source and sulfur powder to grow to obtain the WS2/MoS2Two-dimensional coherent heterojunction network materials. MoTe in large-area single-crystal 2H phase by phase transition2Sulfurizing to generate MoS2Generating high density of gaps, and further growing uniformly oriented WS in the gaps2Thereby obtaining a size that can be largeLarge area, high quality WS at 100 μm2/MoS2Two-dimensional coherent heterojunction network materials. The method is simple to operate, high in repeatability, large in obtained structure area and low in cost, fills the technical vacancy that the area is uncontrollable in the small area and the area in the growth of the two-dimensional coherent heterojunction at present, and has remarkable significance.
Description
Technical Field
The invention belongs to the field of optical or electrical device materials, and relates to a two-dimensional coherent heterojunction network material and a preparation method thereof.
Background
Two-dimensional heterostructures have attracted great research interest to scientists because of extraordinary optical and electronic properties and manual adjustability in their superlattices. On one hand, vertical stacking of transition metal binary halides (TMDs) by van der waals force can adjust characteristics by controlling the stacking order or twist angle, and a morel superlattice exciton state has recently been observed in twisted TMDs, opening the door for research of new quantum electronics and optoelectronics. On the other hand, since they have a similar honeycomb lattice structure, a lateral heterostructure can be formed by bonding TMDs, thereby realizing electronic and optoelectronic characteristic engineering and fabrication of higher performance devices such as transistors, P-diodes, enhancement type photodetectors, and the like. And for the coherent heterostructure, atoms at the interface of the heterostructure share the same crystal lattice, so that the strain caused by lattice mismatch between two different materials can be borne, and a new research tool is provided for adjusting the properties of the two-dimensional heterostructure through strain engineering.
Several methods of synthesizing two-dimensional coherent heterostructures have been reported. Coherent tungsten disulfide (WS) was successfully synthesized using Metal Organic Chemical Vapor Deposition (MOCVD) despite a large lattice mismatch of about 4%2) And tungsten diselenide (WSe)2) The heterojunction provides a platform for the research of strain-induced electronic state transition. MoS is also achieved by a method of Chemical Vapor Deposition (CVD)2/MoSe2、WS2/WSe2、WSe2/MoSe2、WS2/MoS2Single furnace growth and WSe of heterostructures2/MoS2Growing the heterostructure in a second furnace. And combines CVD with other techniques to achieve growth area control for the second material; linear patterns are created, for example, by Focused Ion Beam (FIB) and active edges of TMDs are exposed for secondary growth of the TMDs.
At present, the growth size of the coherent heterojunction is still limited to micron level, and the growth of the coherent heterojunction is randomly distributed on the target substrate, which affects the realization of the mass production target. In addition, fixed point control of a heterojunction growth area can be realized to a certain extent by combining CVD growth with other techniques, but the existing methods such as a secondary electron beam exposure method and a focused ion beam method have high implementation cost and complex operation, and are difficult to realize large-area and low-cost two-dimensional coherent heterostructure production.
Disclosure of Invention
To overcome the disadvantages of the prior art, an object of the present invention is to provide a WS2/MoS2The method for preparing the two-dimensional coherent heterojunction network material comprises the step of growing a large-area two-dimensional heterogeneous material by using a crack caused by stress as a growth substrate to obtain the WS with large particle size2/MoS2A two-dimensional coherent heterojunction material. The preparation method has the advantages of simple preparation conditions, high yield, low cost and good repeatability, and lays a foundation for the large-scale production of two-dimensional heterogeneous materials.
It is another object of the present invention to provide a WS2/MoS2Two-dimensional coherent heterojunction network materials.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
WS (WS)2/MoS2The preparation method of two-dimensional coherent heterojunction network material comprises the steps of carrying out chemical vapor deposition on 2H-phase single crystal MoTe2Carrying out a vulcanization reaction on the layer to obtain a vulcanized product, and reacting the vulcanized product with a tungsten source and sulfur powder to grow to obtain the WS2/MoS2Two-dimensional coherent heterojunction network materials.
Further, the vulcanization reaction is carried out in the inert gas atmosphere, the temperature of the vulcanization reaction is 500-800 ℃, and the time of the vulcanization reaction is 5-60 min.
Preferably, the inert gas is nitrogen or argon; further preferably, the inert gas is argon.
Further, reacting the sulfur powder with the vulcanization product and the tungsten source by taking inert gas as carrier gas under the inert gas atmosphere, wherein the reaction temperature is 760 and 850 ℃, and the reaction time is 2-5 min; the flow rate of the carrier gas is 10-60 sccm.
Further, the tungsten source is tungsten trioxide.
Further, in the reaction of the vulcanization product, a tungsten source and sulfur powder, sodium chloride is mixed and added into the tungsten source, and the mass ratio of the sodium chloride to the tungsten source is 1 (1.5-4).
Further, the single crystal MoTe of 2H phase2The preparation method of the layer comprises the following steps:
spraying a layer of nano molybdenum metal film on the surface of the substrate; carrying out a tellurization reaction on the sublimated Te and a molybdenum metal film by using a carrier gas to obtain the 2H-phase single crystal MoTe2And (3) a layer.
Further, the thickness of the molybdenum metal film is 2-4 nm; the carrier gas in the tellurization reaction is a mixed carrier gas of 4sccm argon and 5sccm hydrogen; the temperature of the tellurization reaction is 500-800 ℃, and the reaction time is 0.5-2 h.
Further, the substrate is one of a silicon wafer, sapphire and a mica sheet, and the surface of the substrate is covered with a silicon oxide layer.
Further, the substrate is subjected to surface treatment in acetone, isopropanol and ethanol respectively by a boiling method, the boiling temperature is 50-100 ℃, and the boiling time is not less than 10 min.
The second purpose of the invention can be achieved by adopting the following technical scheme:
WS (WS)2/MoS2Two-dimensional coherent heterojunction network material, said WS2/MoS2The two-dimensional coherent heterojunction network material is prepared by any one of the methods.
Compared with the prior art, the invention has the beneficial effects that:
1. WS of the present invention2/MoS2Method for preparing two-dimensional coherent heterojunction network material, in chemical vapor deposition, by phase transition to generate large-area single crystal 2H phase MoTe2Sulfurizing to generate MoS2Generating high density of gaps, and further growing uniformly oriented WS in the gaps2Thereby obtaining a large-area and high-quality two-dimensional coherent heterojunction network. The method has the advantages of simple operation, high repeatability, large obtained structure area and low cost, and fills up the defects of the prior two-dimensional coherent heterojunctionThe growth of the medium and small areas has the defect of uncontrollable area technology, and the method has obvious significance.
2. WS of the present invention2/MoS2The two-dimensional coherent heterojunction network material has the size larger than 100 mu m, and is a high-quality in-plane heterojunction network material with large structural area and controllable region.
Drawings
FIG. 1 is a schematic representation of WS of the present invention2/MoS2A growth schematic diagram of the two-dimensional coherent heterojunction network material;
FIG. 2 is a single crystal 2H phase MoTe prepared in example 12An atomic force microscope picture (a) and a Raman spectrogram picture (b);
FIG. 3 is the crack-rich MoS prepared in example 12The atomic force microscope picture and the Raman spectrogram of (a), wherein (b) is an atomic force microscope picture, and (d) is an enlarged view of a dotted line frame in (c), and the Raman spectrogram is built in;
FIG. 4 is WS prepared by example 12/MoS2Atomic force microscopy images (a) (b) and line data images (c) of two-dimensional coherent heterojunction network material;
FIG. 5 WS prepared in example 12/MoS2An atomic force microscopy image (a), a Raman spectrum image (b) and a Raman intensity distribution image (c) of the two-dimensional coherent heterojunction network;
FIG. 6 is two-dimensional coherent WS prepared in example 42/MoS2Atomic force microscopy images (a) (b) and line data images (c) of the heterojunction network;
FIG. 7 is two-dimensional coherent WS prepared in example 52/MoS2Atomic force microscopy of heterojunction networks (a) (b) and line data plot (c).
Detailed Description
The invention will be further described with reference to the accompanying drawings and the detailed description below:
WS (WS)2/MoS2The preparation method of two-dimensional coherent heterojunction network material comprises the steps of carrying out chemical vapor deposition on 2H-phase single crystal MoTe2Carrying out a vulcanization reaction on the layer to obtain a vulcanized product, and reacting the vulcanized product with a tungsten source and sulfur powder to grow to obtain the WS2/MoS2Two-dimensional co-operationA lattice heterojunction network material.
MoTe for large-area single crystal 2H phase generated by phase transition2Sulfurizing, in which S atoms react instead of Te atoms to release internal stress and thus to generate MoS2In the middle of the production of high density gaps, these MoS with high density gaps2Can be used as a growth substrate for growing the WS with uniform orientation in the gap of the substrate2To grow large area WS2/MoS2The purpose of the two-dimensional coherent heterojunction material is.
This process can be carried out by chemical vapor deposition methods and apparatus, which are well known to those skilled in the art.
Further, the vulcanization reaction is carried out in the inert gas atmosphere, the temperature of the vulcanization reaction is 500-800 ℃, and the time of the vulcanization reaction is 5-60 min.
Placing S powder in single crystal MoTe2At the upstream of the layer, sulfur powder is introduced into the reactor for sulfurization under the inert gas carrier gas, so that a large area of single crystal MoS with uniform high-density cracks is obtained2。
Further, reacting the sulfur powder with the vulcanization product and the tungsten source by taking inert gas as carrier gas under the inert gas atmosphere, wherein the reaction temperature is 760 and 850 ℃, and the reaction time is 2-5 min; the flow rate of the carrier gas is 10-60 sccm.
Mixing a tungsten source with MoS2Mixing uniformly, placing sulfur powder at upstream, heating the reaction zone under inert gas atmosphere and certain flow rate, moving the sulfur powder to the edge of the reactor for biochemical heating, introducing the sulfur powder into the reactor under the action of carrier gas to react with tungsten source to obtain the W-rich tungsten sulfide2/MoS2WS of heterogeneous interfaces2/MoS2Two-dimensional coherent heterojunction network
Further, the tungsten source is tungsten trioxide.
Further, in the reaction of the vulcanization product, a tungsten source and sulfur powder, sodium chloride is mixed and added into the tungsten source, and the mass ratio of the sodium chloride to the tungsten source is 1 (1.5-4).
The melting point of a tungsten source, such as tungsten trioxide, can be lowered by mixing sodium chloride with the tungsten source, too little to sublime tungsten trioxide, and too much to overdose the tungsten trioxide.
Further, the single crystal MoTe of 2H phase2The preparation method of the layer comprises the following steps:
spraying a layer of nano molybdenum metal film on the surface of the substrate; carrying out a tellurization reaction on the sublimated Te and a molybdenum metal film by using a carrier gas to obtain the 2H-phase single crystal MoTe2And (3) a layer.
Placing nano-grade molybdenum metal, tellurium powder and sulfur powder in a normal-pressure tube furnace, introducing a certain amount of argon and hydrogen to react for a period of time for tellurization, and reacting the molybdenum metal film into 1T' phase polycrystalline MoTe after tellurization2Single crystal MoTe phase-converted to 2H phase2。
Further, the thickness of the molybdenum metal film is 2-4 nm; the carrier gas in the tellurization reaction is a mixed carrier gas of 4sccm argon and 5sccm hydrogen; the temperature of the tellurization reaction is 500-800 ℃, and the reaction time is 0.5-2 h.
The thickness of the molybdenum metal film is 2-4nm, so that the phenomenon that the film cannot be formed when the thickness is too small and the two-dimensional characteristic is lost when the thickness is too large is avoided; preferably, the thickness of the molybdenum metal film is 3 nm. The molybdenum metal film may be sprayed by magnetic sputtering, or by conventional spraying methods such as electron beam deposition or thermal deposition.
Further, the substrate is one of a silicon wafer, sapphire and a mica sheet, and the surface of the substrate is covered with a silicon oxide layer.
The substrate can be a silicon wafer, sapphire or mica sheet, the surface of the substrate is covered with a silicon oxide layer, and the selection of the substrate depends on the subsequent use scene. Preferably, the substrate is a 500 μm thick silicon wafer having a surface covered with 280nm silicon oxide.
Further, the substrate is subjected to surface treatment in acetone, isopropanol and ethanol respectively by a boiling method, the boiling temperature is 50-100 ℃, and the boiling time is not less than 10 min.
The substrate needs to be pretreated, and the surface impurities are removed by adopting an organic solution boiling method. Preferably, the silicon wafer is boiled at 80 ℃ for not less than 20min by using organic solvents respectively comprising acetone, isopropanol and ethanol, and impurities such as organic residues on the surface of the silicon wafer are removed. And then washing with deionized water and blow-drying with a nitrogen gun to obtain the clean substrate with the surface being pretreated.
Preparation of WS2/MoS2The flow of the two-dimensional coherent heterojunction network material is shown in fig. 1, and we will now describe the preparation process by using specific examples.
Example 1:
1cm of silicon wafer with gamma of 1cm is sequentially soaked in acetone, isopropanol and ethanol at 80 deg.C for 20min, cleaned, and plated with molybdenum with thickness of 3nm as growth substrate. 300mg of tellurium powder and 60mg of sulfur powder are respectively placed at the upstream of the silicon wafer, an argon gas valve is opened, the flow rate is adjusted to be 200sccm, the argon gas valve is kept for 5 minutes, and residual oxygen in the tube furnace is removed. Adjusting the flow rates of argon and hydrogen to be 4sccm and 5sccm respectively, opening a heating switch of the furnace to heat the temperature in the reaction region to 660 ℃ within 15min, heating the tellurium powder to sublimate, and keeping the tellurium powder to grow for 1 h. And (3) enabling sulfur powder to enter the edge of the furnace, closing hydrogen, regulating the flow of argon gas to 30sccm, and introducing the sulfur powder into the tubular furnace through a magnet under the argon gas carrier gas of 30sccm to perform a vulcanization reaction for 10 min. After the reaction is finished, the tubular furnace is closed for heating, and the argon flow is adjusted to 200sccm for rapid cooling. Thereby obtaining a large-area single crystal MoS with uniform high-density cracks2。
The obtained MoS2Placed as a new growth substrate in a tube furnace, inverted on a quartz boat loaded with mixed particles of 4mg of tungsten oxide and 0.45mg of sodium chloride, and placed upstream with 30mg of sulfur powder. Argon gas was adjusted to 30sccm and heating of the tube furnace was started so that the temperature in the reaction zone was heated to 800 ℃ within 20 min. Pushing the sulfur powder into the edge of the tube furnace, reacting for 3min, and horizontally moving the tube furnace to stop heating the sulfur powder. And (4) closing the tubular furnace for heating, and adjusting the argon flow to 200sccm for rapid cooling. Taking out the sample after the tube furnace is cooled to room temperature to obtain the WS-enriched solution2/MoS2Two-dimensional coherent heterojunction networks of heterointerfaces.
Example 2:
1cm of silica wafer of gamma 1cm is sequentially treated with acetone, isopropanol,soaking in ethanol for 30min, cleaning, and plating molybdenum with thickness of 4nm as growth substrate. 400mg of tellurium powder and 60mg of sulfur powder are respectively placed at the upstream of the silicon wafer, an argon gas valve is opened, the flow rate is adjusted to be 150sccm, the argon gas valve is kept for 10 minutes, and residual oxygen in the tube furnace is removed. Regulating the flow rates of argon and hydrogen to be 4sccm and 5sccm respectively, turning on a heating switch of the furnace to heat the temperature in the reaction region to 500 ℃ within 10min, heating the tellurium powder to sublimate, and keeping the tellurium powder to grow for 2 h. And (3) enabling sulfur powder to enter the edge of the furnace, closing hydrogen, regulating the flow of argon gas to 50sccm, and introducing the sulfur powder into the tubular furnace through a magnet under the argon gas carrier gas of 50sccm to perform a vulcanization reaction for 5 min. After the reaction is finished, the tubular furnace is closed for heating, and the argon flow is adjusted to 150sccm for rapid cooling. Thereby obtaining a large-area single crystal MoS with uniform high-density cracks2。
The obtained MoS2Placed as a new growth substrate in a tube furnace, inverted on a quartz boat loaded with mixed particles of 4mg of tungsten oxide and 0.3mg of sodium chloride, and placed upstream with 30mg of sulfur powder. Argon was adjusted to 30sccm and heating of the tube furnace was started so that the temperature in the reaction zone was heated to 760 ℃ within 15 min. Pushing the sulfur powder into the edge of the tube furnace, reacting for 5min, and horizontally moving the tube furnace to stop heating the sulfur powder. The tube furnace is closed to heat, and the argon flow is adjusted to 150sccm to rapidly cool. Taking out the sample after the tube furnace is cooled to room temperature to obtain the WS-enriched solution2/MoS2Two-dimensional coherent heterojunction networks of heterointerfaces.
Example 3:
a1 cm gamma 1cm silicon wafer is sequentially soaked in acetone, isopropanol and ethanol at 100 deg.C for 10min, cleaned, and plated with 2nm thick molybdenum as growth substrate. 350mg of tellurium powder and 60mg of sulfur powder are respectively placed at the upstream of the silicon wafer, an argon gas valve is opened, the flow rate is adjusted to be 250sccm, the argon gas valve is kept for 3 minutes, and residual oxygen in the tubular furnace is removed. Adjusting the flow rates of argon and hydrogen to be 4sccm and 5sccm respectively, opening a heating switch of the furnace to heat the temperature in the reaction region to 800 ℃ within 20min, heating the tellurium powder to sublimate, and keeping the growth for 0.5 h. Making sulfur powder enter the edge of the furnace, closing hydrogen, regulating argon flow to 10sccm, and passing the sulfur powder through a magnet under the argon carrier gas of 10sccmIntroducing into a tube furnace for sulfurization reaction for 20 min. After the reaction is finished, the tubular furnace is closed for heating, and the argon flow is adjusted to 250sccm for rapid cooling. Thereby obtaining a large-area single crystal MoS with uniform high-density cracks2。
The obtained MoS2Placed as a new growth substrate in a tube furnace, inverted on a quartz boat loaded with mixed particles of 4mg of tungsten oxide and 0.6mg of sodium chloride, and placed upstream with 30mg of sulfur powder. Argon was adjusted to 30sccm and heating of the tube furnace was started so that the temperature in the reaction zone was heated to 850 ℃ within 20 min. Pushing the sulfur powder into the edge of the tube furnace, reacting for 2min, and horizontally moving the tube furnace to stop heating the sulfur powder. The tube furnace is closed to heat, and the argon flow is adjusted to 250sccm to rapidly cool. Taking out the sample after the tube furnace is cooled to room temperature to obtain the WS-enriched solution2/MoS2Two-dimensional coherent heterojunction networks of heterointerfaces.
Example 4:
example 4 differs from example 1 in that WS in example 12During the growth process, the flow of argon gas was adjusted to 10sccm, and the remaining process parameters were exactly the same as in example 1.
Example 5:
example 5 differs from example 1 in that WS in example 12During the growth, the argon flow was adjusted to 50sccm, and the remaining process parameters were exactly the same as in example 1.
Crack-rich MoS prepared as in example 1 of FIG. 32As shown in the atomic force microscope images (c) and the enlarged view of the broken line frame in (c) (d), after the vulcanization, a crack-rich single crystal MoS was observed2In the Raman spectrum chart built in (d), a region of 378cm was observed-1And 402cm-1Characteristic peak of (2) indicating that MoS is obtained2And (4) crystals.
WS prepared as example 1 of FIG. 52/MoS2Atomic force microscope (a) of two-dimensional coherent heterojunction network Material, in WS2After growth, the original MoS was observed2Filled with white crystals, FIG. 5 WS prepared in example 12/MoS2The Raman spectrum diagram (b) of the two-dimensional coherent heterojunction network material can obtain that the characteristic peak of the white crystal is 355cm-1And 420cm-1The white crystal is stated to be WS2And (4) crystals. And WS prepared from example 1 of FIG. 52/MoS2The Raman intensity distribution graph (c) of the two-dimensional coherent heterojunction network material can observe the Raman peak position distribution with clear outline, which indicates that the two-dimensional coherent heterojunction network material is a high-quality in-plane heterojunction. WS prepared from example 1 of FIG. 42/MoS2The atomic force microscopy (a) (b) and the line data graph (c) of the two-dimensional coherent heterojunction network material can also see WS2High quality growth along the gap.
Two-dimensional coherent WS prepared by FIG. 6, example 42/MoS2The heterojunction network is shown in atomic force microscopy images (a) and (b) and line data graph (c), and the secondarily grown WS is seen under the condition of 10sccm Ar gas carrier gas2Can not completely fill original MoS2Such that WS2There was a collapse at the crystal.
Two-dimensional coherent WS prepared by FIG. 7, example 52/MoS2The heterojunction network is shown in atomic force microscopy images (a) and (b) and line data graph (c), and the secondarily grown WS is seen under the condition of 50sccm Ar gas carrier gas2Overgrowth of significantly greater growth height than MoS2Planar and in MoS2Can also find WS2And (4) nucleating and growing crystals.
Thus, by comparing FIG. 3 with FIG. 5 and FIG. 6, it can be seen that the WS is passed2The flow of carrier gas in the growth process can effectively regulate and control WS2Thereby controlling WS2/MoS2Morphology of two-dimensional coherent heterojunction growth.
In summary, the present application provides a WS2/MoS2The preparation method of the two-dimensional coherent heterojunction network material can obtain a large-area and high-quality two-dimensional coherent heterojunction network; the method is simple to operate, high in repeatability and large in obtained structure area, fills the technical vacancy that the area is uncontrollable and the small area is small in the growth of the two-dimensional coherent heterojunction at present, and has obvious significance.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Claims (10)
1. WS (WS)2/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
by chemical vapor deposition of 2H phase of single crystal MoTe2Carrying out a vulcanization reaction on the layer to obtain a vulcanized product, and reacting the vulcanized product with a tungsten source and sulfur powder to grow to obtain the WS2/MoS2Two-dimensional coherent heterojunction network materials.
2. WS according to claim 12/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
the sulfuration reaction is carried out in the inert gas atmosphere, the temperature of the sulfuration reaction is 500-800 ℃, and the time of the sulfuration reaction is 5-60 min.
3. WS according to claim 12/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
reacting sulfur powder with a vulcanization product and a tungsten source by taking inert gas as carrier gas under the inert gas atmosphere, wherein the reaction temperature is 760-; the flow rate of the carrier gas is 10-60 sccm.
4. WS according to claim 12/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
the tungsten source is tungsten trioxide.
5. A WS according to any of claims 1-42/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
in the reaction of the vulcanization product, a tungsten source and sulfur powder, sodium chloride is mixed and added into the tungsten source, and the mass ratio of the sodium chloride to the tungsten source is 1 (1.5-4).
6. WS according to claim 12/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
the 2H phase of single crystal MoTe2The preparation method of the layer comprises the following steps:
spraying a layer of nano molybdenum metal film on the surface of the substrate; carrying out a tellurization reaction on the sublimated Te and a molybdenum metal film by using a carrier gas to obtain the 2H-phase single crystal MoTe2And (3) a layer.
7. WS according to claim 62/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
the thickness of the molybdenum metal film is 2-4 nm; the carrier gas in the tellurization reaction is a mixed carrier gas of 4sccm argon and 5sccm hydrogen; the temperature of the tellurization reaction is 500-800 ℃, and the reaction time is 0.5-2 h.
8. WS according to claim 62/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
the substrate is one of a silicon wafer, sapphire and a mica sheet, and the surface of the substrate is covered with a silicon oxide layer.
9. WS according to claim 62/MoS2A preparation method of a two-dimensional coherent heterojunction network material is characterized in that,
the substrate is subjected to surface treatment in acetone, isopropanol and ethanol respectively by a boiling method, the boiling temperature is 50-100 ℃, and the boiling time is not less than 10 min.
10. WS (WS)2/MoS2Two-dimensional coherent heterojunction network material, wherein said WS is2/MoS2The two-dimensional coherent heterojunction network material is prepared by the method of any one of claims 1 to 9.
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