CN116926472A - Method for growing multilayer two-dimensional material van der Waals heterojunction by lamination - Google Patents
Method for growing multilayer two-dimensional material van der Waals heterojunction by lamination Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000003475 lamination Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 98
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000012159 carrier gas Substances 0.000 claims description 18
- 229910052594 sapphire Inorganic materials 0.000 claims description 18
- 239000010980 sapphire Substances 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 150000003623 transition metal compounds Chemical class 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 238000007740 vapor deposition Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000002207 thermal evaporation Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000026045 iodination Effects 0.000 claims description 2
- 238000006192 iodination reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000000059 patterning Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- 239000011593 sulfur Substances 0.000 description 21
- 239000010453 quartz Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- 238000000137 annealing Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 9
- 238000011144 upstream manufacturing Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 229910016001 MoSe Inorganic materials 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal chalcogenide Chemical class 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000013341 scale-up Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5866—Treatment with sulfur, selenium or tellurium
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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
- 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
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Abstract
The invention discloses a method for growing a multi-layer two-dimensional material van der Waals heterojunction by lamination. In addition, the invention prepares the metal film from physical vapor deposition, and the target product is obtained through chemical vapor deposition, so that the amount of raw materials participating in the reaction is controlled, raw materials are hardly wasted, and compared with the traditional method, the utilization rate of the raw materials is greatly improved, the crystal quality of the product is greatly improved, and meanwhile, the product has extremely strong atmospheric environmental stability. The size of the prepared Van der Waals heterojunction film can reach the wafer level, patterning growth can be realized, the method has important significance for large-scale production and application, and the successful preparation of various Van der Waals heterojunction film materials provides material preparation technical support for the development of the fields of photoelectric devices, spin quantum devices and the like.
Description
Technical Field
The invention belongs to the technical field of two-dimensional material preparation, and relates to a method for growing a multi-layer two-dimensional material Van der Waals heterojunction by lamination, in particular to a method for preparing a large-size Van der Waals heterojunction and researching physical properties by combining physical vapor deposition and chemical vapor deposition, and realizing layer-by-layer growth by precisely controlling reaction temperature and reaction products of each step, wherein the wafer-level, layer-number-controllable and multi-kind high-quality Van der Waals heterojunction film is finally prepared.
Background
In recent years, two-dimensional materials have exhibited a wealth of physical and chemical properties, including semiconductors, metals, magnetic properties, superconductivity, and the like. Therefore, in order to search for new materials and realize performance improvement of functional devices, combining two-dimensional materials into van der waals heterostructures has become a promising research hotspot in recent years. Despite this direction of research, most van der waals heterojunction materials are still obtained by vertically stacking two-dimensional materials peeled off by a multiple transfer method. However, such a method based on mechanical lift-off and manual re-stacking is difficult to apply to device scale-up, and there may be cases where interfacial impurities are introduced even during transfer. It is therefore important to explore a method of preparation that can stack different layered materials together by direct epitaxial growth to form a clean van der waals heterojunction interface.
At present, almost all research is focused on semiconductor van der waals heterojunctions and is limited to the simplest double layer heterostructures achieved by selecting a specific combination of materials. This is mainly because superconductor two-dimensional materials with good stability were not available in previous van der waals heterojunction fabrication methods, and growing complex heterostructures with three or more different materials also requires that the material of each layer be sufficiently stable and intact to be fully preserved during the subsequent growth process. The multifunctional multilayer van der Waals heterostructure superimposes semiconductor and superconductor materials with different properties, and can realize functions which cannot be achieved by other semiconductor heterostructures which can be prepared at present. However, such multi-layer heterostructures for versatility have not been achieved to date, and free growth of van der waals heterojunction has not been achieved even more in the current state of the art.
Disclosure of Invention
The invention aims to: the technical problem to be solved by the invention is to provide a method for growing a multilayer two-dimensional van der Waals heterojunction by lamination, which combines physical vapor deposition and chemical vapor deposition, realizes layer-by-layer growth by precisely controlling the growth temperature, prepares a wafer-level high-quality van der Waals heterojunction film, and can be used as an ideal method for nano device assembly and basic research.
The technical scheme is as follows: in order to solve the technical problems, the invention provides a method for growing a multilayer two-dimensional van der Waals heterojunction in a lamination manner, which comprises the following steps:
(1) Deposition preparation of a metal precursor film: on a flat substrate (the flat substrate comprises C-plane sapphire or SiO) 2 A Si substrate) is deposited with a layer of metal film with high flatness and high crystallinity as a precursor;
(2) Preparation of a first layer transition metal compound film: placing the precursor obtained in the step (1) in a heating furnace, regulating carrier gas flow, temperature and pressure, heating the nonmetallic precursor to sublimate into a gaseous state, moving a constant-temperature heating position to the position of the metallic precursor to promote vapor deposition reaction, closing heating of the nonmetallic precursor after the reaction is finished, naturally cooling reactants, and completing preparation of the first layer of transition metal compound when the temperature is reduced to room temperature;
(3) And (3) preparing a metal precursor film by secondary deposition: depositing a second layer of metal precursor on the grown first layer of compound film by using a physical vapor deposition method;
(4) Preparation of a second layer transition metal compound film: placing the second layer of metal precursor in the step (3) in a chemical vapor deposition device, regulating the temperature, the carrier gas flow and the pressure, setting the growth temperature not higher than the growth temperature of the first layer of transition metal compound film, heating the nonmetallic precursor to sublimate into a gas state, moving a constant-temperature heating position to the position of the metal precursor, promoting vapor deposition reaction, and setting the reaction time; after the reaction is finished, heating the nonmetallic precursor is closed, simultaneously, naturally cooling reactants, and after the temperature is reduced to room temperature, preparing the second layer of transition metal compound;
(5) Lamination growth of multilayer two-dimensional van der waals heterojunction: changing the type of the deposited metal film and the precursor, and repeating the preparation processes of the steps (1) - (2).
In the step (1), the physical vapor deposition method comprises one or more of a magnetron sputtering process, a thermal evaporation process, an electron beam evaporation process or a pulse laser deposition process.
Wherein in step (1), the substrate includes, but is not limited to, silicon wafer or sapphire.
Wherein in the step (1), high flatness and high crystallinity mean that the average is 100 μm 2 The fluctuation is within + -0.5 nm, and the grain size is 10-50 μm, including one or more of Mo, W, nb, ti, V, ta, pt.
Wherein, in the step (1), when the physical vapor deposition method is a magnetron sputtering process, the parameter is that the pressure is 0.1 to 500Pa, the carrier gas is one or more of nitrogen, argon, oxygen or hydrogen, the film deposition rate is 0.01 to 10nm/s, the substrate temperature is 20 to 800 ℃, and the thickness of the metal film is 0.5 to 100nm;
wherein in the step (1), when the physical vapor deposition method is a thermal evaporation, electron beam evaporation or pulse laser deposition process, the parameters are that the pressure is less than 10 -4 Pa, the film deposition rate is 0.01-10 nm/s, the substrate heating is 20-800 ℃, and the thickness of the metal film is 0.5-100 nm.
Wherein in the step (2), the nonmetallic precursor is S, se, te, I 2 Or Br (Br) 2 One of them.
Wherein in the step (2), the vapor deposition reaction comprises one or more of sulfuration, selenization, tellurion, iodination or bromination.
Wherein in the step (2) or (4), the vapor deposition reaction temperature is 50-800 ℃, and the preferable range is 400-800 ℃; pressure of 10 -5 ～10 5 Pa, a preferable range is 10 -2 ～10 5 Pa; the carrier gas being nitrogenArgon, hydrogen or an inert gas; the air flow is 5-200 sccm, and the preferable range is 20-100 sccm; the thickness of the product film is 0.5-100 nm.
The annealing treatment of the reacted sample in the invention comprises the following steps: the temperature is 50-800 ℃, and the preferable range is 200-700 ℃; pressure of 10 -5 ～10 5 Pa, a preferable range is 10 -5 0.1Pa; the carrier gas can be reducing or inert gases such as nitrogen, argon, hydrogen and the like; the air flow rate is 5 to 200sccm, preferably 20 to 200sccm.
Wherein the metal film comprises one or more of Mo, W, nb, ti, V, ta, pt.
The size of the sample in the present invention is in the range of 1 μm to 1000cm, preferably in the range of-1 to 20cm.
The sample shape in the present invention can be customizable, as well as complex patterning, which is required when the step involves physical vapor deposition.
In the present invention, the ambient temperature is 20 to 50℃and the preferable range is 20 to 30 ℃.
The size of the prepared Van der Waals heterojunction film can reach the wafer level, patterning growth can be realized, the method has important significance for large-scale production and application, and the successful preparation of various Van der Waals heterojunction film materials provides material preparation technical support for the development of the fields of photoelectric devices, spin quantum devices and the like.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. according to the invention, a physical vapor deposition method is adopted to deposit the metal film until chemical vapor deposition is adopted to obtain a target product, so that the amount of raw materials participating in the reaction is controlled, almost no raw materials are wasted, different van der Waals heterojunction materials with different configurations can be prepared by changing different metal deposition films and growing precursors according to application research requirements, the designability and flexibility are high, the finally deposited film is smooth, the quality of a sample is ensured, the utilization rate of the raw materials is greatly improved, the crystal quality of the product is greatly improved, and meanwhile, the product has extremely strong atmospheric environment stability.
2. The invention effectively controls the thickness and the crystallinity of the metal film by adjusting the speed and the temperature of the substrate during physical vapor deposition,
3. the invention combines the metal film with other nonmetallic elements by using a chemical vapor deposition method, thereby ensuring the cleanliness and quality of the sample.
4. The invention designs a post-treatment step to effectively remove redundant substances on the surface of the sample.
5. The method is a universal method, can break through the prior art difficulties, realizes free stacking growth of various types of Van der Waals heterojunction films, can prepare wafer-level, multi-layer and multi-kind high-quality two-dimensional Van der Waals heterojunction materials, can realize patterned growth, is not limited to materials with specific properties or lattice structures, has important significance for large-scale production application, successfully prepares various functional Van der Waals heterojunction film materials, and provides material preparation technical support for development of fields such as photoelectric devices, spin quantum devices and the like.
Drawings
FIG. 1 two-layer WS prepared 2 /MoS 2 Van der waals heterojunction thin films: a, two-layer WS 2 /MoS 2 Optical microscopy of van der waals heterogeneous thin films on sapphire substrates; b, two-layer WS 2 /MoS 2 Atomic force microscope pictures of Van der Waals heterogeneous films on silicon wafer substrates; c, a corresponding height section view of the atomic force microscope.
FIG. 2, prepared three-layered WS 2 /MoS 2 /MoSe 2 Van der waals heterojunction thin films: a, a four inch film photo grown by taking sapphire as a substrate; b, atomic force microscope pictures; c, a corresponding height section view of the atomic force microscope.
FIG. 3 prepared four-layer WS 2 /MoS 2 /MoSe 2 /NbSe 2 And five-layer WS 2 /MoS 2 /MoSe 2 /NbSe 2 /PtTe 2 Van der waals heterojunction thin films: a, a photo of a four-layer film grown by taking four-inch sapphire as a substrate; b, byA four-inch silicon wafer is a photo of a four-layer film grown on a substrate; c, taking a five-layer film photo grown by taking four-inch sapphire as a substrate; and d, a five-layer film photo grown by taking four-inch sapphire as a substrate.
Fig. 4, general process of growing two-dimensional van der waals heterojunction by lamination.
Detailed Description
Example 1 WS on sapphire substrate 2 /MoS 2 Preparation of double-layer Van der Waals heterojunction film
The method for growing the double-layer two-dimensional material van der Waals heterojunction on the sapphire substrate through lamination comprises the following steps: placing the sapphire substrate on a tray of a magnetron sputtering reaction chamber by taking high-purity tungsten metal as a target material, and waiting for the pressure intensity of the reaction chamber to be less than 10 - 4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and evaporation time of 20s. The tungsten metal film was placed in a quartz tube of a tube furnace, and a sulfur source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the sulfur source is 160 ℃, the temperature of the metal film is 800 ℃, the carrier gas is 100sccm of argon, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. And after 60 minutes, rapidly cooling the quartz tube to obtain the first layer of film tungsten sulfide. Placing the first layer of film product on a tray of a magnetron sputtering reaction chamber until the pressure of the reaction chamber is less than 10 - 4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and evaporation time of 20s. The molybdenum metal film was placed in the quartz tube of the tube furnace and the sulfur source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the sulfur source is 160 ℃, the temperature of the metal film is 700 ℃, the carrier gas is 100sccm of argon, 150sccm of hydrogen, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. After 60 minutes, the quartz tube is cooled rapidly, and the product tungsten sulfide/molybdenum sulfide double-layer van der Waals heterojunction film is obtained, as shown in figure 1a.
EXAMPLE 2SiO 2 Preparation of tungsten sulfide/molybdenum sulfide double-layer van der Waals heterojunction film on Si substrate
Growth on SiO by lamination 2 A method of double layer two-dimensional material van der Waals heterojunction on Si substrate. The method comprises the following steps: siO with high-purity tungsten metal as target material 2 Placing Si substrate on tray of magnetron sputtering reaction chamber until reaction chamber pressure is less than 10 - 4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and evaporation time of 20s. The tungsten metal film was placed in a quartz tube of a tube furnace, and a sulfur source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the sulfur source is 160 ℃, the temperature of the metal film is 800 ℃, the carrier gas is 100sccm of argon, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. And after 60 minutes, rapidly cooling the quartz tube to obtain the first layer of film tungsten sulfide. Placing the first layer of film product on a tray of a magnetron sputtering reaction chamber until the pressure of the reaction chamber is less than 10 - 4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and evaporation time of 20s. The molybdenum metal film was placed in the quartz tube of the tube furnace and the sulfur source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the sulfur source is 160 ℃, the temperature of the metal film is 700 ℃, the carrier gas is 100sccm of argon, 150sccm of hydrogen, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. After 60 minutes, the quartz tube was rapidly cooled to obtain the product tungsten sulfide/molybdenum sulfide double-layer van der Waals heterojunction film, as shown in FIGS. 1b and 1c.
Example 3
The thickness-controllable double-layer van der Waals heterojunction (in this embodiment, the thickness of each layer of sample can be 1 nm-10 nm) is prepared by a lamination growth method, specifically: siO is prepared from high-purity metal (Ti, mo, nb, ta, etc) 2 Placing Si substrate on tray of magnetron sputtering reaction chamber until reaction chamber pressure is less than 10 -4 Pa, heating to 200 ℃, coating pressure being 5Pa, coating speed being 0.05nm/s, controlling thickness of the film by changing coating time, and adjusting the coating time to be 20-200 s. The metal film was placed in a quartz tube of a tube furnace, and a sulfur source was placed upstream of the metal film. In the compounding reaction, the heating temperature of the sulfur source is 160 ℃, and the temperature of the metal film is 8%The reaction was completed after 30 minutes at 00℃with 100sccm argon and 100sccm hydrogen as carrier gas. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. After 60 minutes, the quartz tube is cooled rapidly, and the first layer of film of the product is obtained. Placing the first layer of film product on a tray of a magnetron sputtering reaction chamber until the pressure of the reaction chamber is less than 10 -4 Pa, heating to 200 ℃, coating pressure being 5Pa, coating speed being 0.05nm/s, controlling thickness of the film by changing coating time, and adjusting the coating time to be 20-200 s. The metal film was placed in the quartz tube of the tube furnace and a selenium source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the selenium source is 350 ℃, the temperature of the metal film is 700 ℃, the carrier gas is 100sccm of argon, 150sccm of hydrogen, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the selenium source, and carrying out annealing treatment at 350 ℃ on the sample in situ. And after 60 minutes, rapidly cooling the quartz tube to obtain the two layers of van der Waals heterojunction films.
Example 4 growth of a three-layer Van der Waals heterojunction film on a sapphire substrate
Three layers of van der waals heterojunction (in this embodiment, a first layer of metal film is deposited on the sapphire substrate) are prepared on the sapphire substrate by a stack growth method, specifically: taking high-purity tungsten metal as a target material, placing a sapphire substrate on a tray of a magnetron sputtering reaction chamber, and waiting for the pressure intensity of the reaction chamber to be less than 10 -4 Pa, heating to 400 ℃, coating pressure of 10Pa, coating speed of 0.02nm/s and evaporation time of 20s. The metal film was placed in a quartz tube of a tube furnace, and a sulfur source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the sulfur source is 160 ℃, the temperature of the metal film is 800 ℃, the carrier gas is 100sccm of argon, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. And after 60 minutes, rapidly cooling the quartz tube to obtain the first layer of film tungsten sulfide. Putting the first layer of film product on a tray of a magnetron sputtering reaction chamber, evaporating molybdenum metal, and keeping the pressure of the reaction chamber to be less than 10 -4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and evaporation time of 20s. The metal film is put into a quartz tube of a tube furnace,a sulfur source is placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the sulfur source is 160 ℃, the temperature of the metal film is 700 ℃, the carrier gas is 100sccm of argon, 150sccm of hydrogen, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the sulfur source, and carrying out annealing treatment at 350 ℃ on the sample in situ. Evaporating molybdenum metal again until the pressure of the reaction chamber is less than 10 -4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and evaporation time of 20s. The metal film was placed in the quartz tube of the tube furnace and a selenium source was placed upstream of the metal film. In the chemical combination reaction, the heating temperature of the selenium source is 350 ℃, the temperature of the metal film is 700 ℃, the carrier gas is 100sccm of argon, 150sccm of hydrogen, and the reaction is finished after 30 minutes. Rapidly reducing the temperature of the selenium source, and carrying out annealing treatment at 350 ℃ on the sample in situ. After 60 minutes, the quartz tube was rapidly cooled to obtain a product, a three-layer van der waals heterojunction film, as shown in fig. 2.
Example 5
The method of this example is based on example 1 or 2, and the multilayer van der waals heterojunction of transition metal chalcogenide is prepared by a layer growth method specifically: in this embodiment, the high purity metal including tungsten, molybdenum, niobium, and platinum is C-plane sapphire or SiO 2 Placing Si substrate on tray of magnetron sputtering reaction chamber until reaction chamber pressure is less than 10 -4 Pa, heating to 200 ℃, coating pressure of 5Pa, coating speed of 0.05nm/s and coating time of 20s. Multiple sulfidation, selenization, and tellurization (in this example, the precursor used for chemical vapor deposition includes tellurion, "growth preparation of tellurion" herein, see, e.g., zhou, Z., xu, T., zhang, C.et al, enhancing stability by tuning element ratio in 2D transition metal chalcogenides.Nano Res.2021, 14, 1704-1710)]) In this embodiment, the reaction temperature of the two-dimensional material grown successively is not higher than the reaction temperature of the last grown product, so as to obtain the multilayer van der waals heterojunction film. As shown in fig. 3a-3d, four and five layers of van der waals films are shown grown on sapphire and silicon wafer substrates.
Example 6
The method of the embodiment canReferring to example 1 or 5, a general procedure for preparing a multi-layered van der waals heterojunction containing various kinds of transition metal chalcogenides by a layer growth method is as follows: the high purity metal is used as a target material, and the metal comprises but is not limited to titanium, molybdenum, niobium, tantalum, platinum and the like, and a substrate (C-plane sapphire or SiO 2 Si substrate) is placed on a tray of a magnetron sputtering reaction chamber until the pressure of the reaction chamber is less than 10 -4 Pa, heating to 200 ℃, coating pressure being 5Pa, coating speed being 0.05nm/s, and controlling thickness of the film to be 1-10nm by changing coating time. The metal film is put into a quartz tube of a tube furnace to react at a certain temperature. And placing the first layer of film product on a tray of a magnetron sputtering reaction chamber, continuously evaporating a second layer of metal, and controlling the thickness of the film by changing the film-plating time. And (3) placing the metal film into a quartz tube of a tube furnace, and carrying out chemical reaction again. Repeating the above operation for a plurality of times, the reaction temperature of the two-dimensional material which is grown successively is not higher than the reaction temperature of the last growth product, and a multilayer van der Waals heterojunction film can be obtained, as shown in fig. 4.
Claims (10)
1. A method of growing a multilayer two-dimensional van der waals heterojunction in a stack, the method comprising the steps of:
(1) Deposition preparation of a metal precursor film: depositing a layer of metal film with high flatness and high crystallinity on a flat substrate by using a physical vapor deposition method as a precursor;
(2) Preparation of a first layer transition metal compound film: placing the precursor obtained in the step (1) in a heating furnace, regulating carrier gas flow, temperature and pressure, heating the nonmetallic precursor to sublimate into a gaseous state, moving a constant-temperature heating position to the position of the metallic precursor to promote vapor deposition reaction, closing heating of the nonmetallic precursor after the reaction is finished, naturally cooling reactants, and completing preparation of the first layer of transition metal compound when the temperature is reduced to room temperature;
(3) And (3) preparing a metal precursor film by secondary deposition: depositing a second layer of metal precursor on the grown first layer of compound film by using a physical vapor deposition method;
(4) Preparation of a second layer transition metal compound film: placing the second layer of metal precursor in the step (3) in a chemical vapor deposition device, regulating the temperature, the carrier gas flow and the pressure, setting the growth temperature not higher than the growth temperature of the first layer of transition metal compound film, heating the nonmetallic precursor to sublimate into a gas state, moving a constant-temperature heating position to the position of the metal precursor, promoting vapor deposition reaction, and setting the reaction time; after the reaction is finished, heating the nonmetallic precursor is closed, simultaneously, naturally cooling reactants, and after the temperature is reduced to room temperature, preparing the second layer of transition metal compound;
(5) Lamination growth of multilayer two-dimensional van der waals heterojunction: changing the type of the deposited metal film and the precursor, and repeating the preparation processes of the steps (1) - (2).
2. The method of claim 1, wherein in step (1), the physical vapor deposition method comprises using one or more of a magnetron sputtering process, a thermal evaporation process, an electron beam evaporation process, or a pulsed laser deposition process.
3. The method of growing a multilayer two-dimensional van der waals heterojunction as claimed in claim 1, wherein in step (1), the substrate comprises silicon wafer or sapphire.
4. The method of claim 1, wherein in step (1), the metal thin film having high flatness and high crystallinity comprises one or more of Mo, W, nb, ti, V, ta, pt.
5. The method for growing a multilayer two-dimensional van der waals heterojunction according to claim 2, wherein in the step (1), when the physical vapor deposition method is a magnetron sputtering process, the parameters are that the pressure is 0.1 to 500Pa, the carrier gas is one or more of nitrogen, argon, oxygen or hydrogen, the film deposition rate is 0.01 to 10nm/s, the substrate temperature is 20 to 800 ℃, and the thickness of the metal film is 0.5 to 100nm.
6. The method of claim 2, wherein in step (1), when the physical vapor deposition method is a thermal evaporation, electron beam evaporation or pulsed laser deposition process, the parameters are pressure<10 -4 Pa, the film deposition rate is 0.01-10 nm/s, the substrate heating is 20-800 ℃, and the metal film thickness is 0.5-100 nm.
7. The method of growing a multilayer two-dimensional van der waals heterojunction as claimed in claim 2, wherein in step (2), the nonmetallic precursor is S, se, te, I 2 Or Br (Br) 2 One of them.
8. The method of claim 2, wherein in step (2), the vapor deposition reaction comprises one or more of a sulfidation, selenization, tellurion, iodination, or bromination reaction.
9. The method of growing a multilayer two-dimensional van der waals heterojunction as claimed in claim 1, wherein in the step (2) or (4), the vapor deposition reaction temperature is 50 to 800 ℃; pressure of 10 -5 ~ 10 5 Pa; the carrier gas is nitrogen, argon, hydrogen or inert gas; the air flow is 5-200 sccm; the thickness of the product film is 0.5-100 nm.
10. The method of growing a multilayer two-dimensional van der waals heterojunction as claimed in claim 1, wherein the metal film species comprises one or more of Mo, W, nb, ti, V, ta, pt.
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