CN114855144A - Transition metal chalcogenide thin-layer material and preparation method and application thereof - Google Patents
Transition metal chalcogenide thin-layer material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 92
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 74
- -1 Transition metal chalcogenide Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
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- 239000002086 nanomaterial Substances 0.000 claims abstract description 8
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- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 21
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- 229910052798 chalcogen Inorganic materials 0.000 claims description 15
- 150000001787 chalcogens Chemical class 0.000 claims description 15
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- 238000004321 preservation Methods 0.000 claims description 10
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- 238000001816 cooling Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 150000002496 iodine Chemical class 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 7
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- 150000004770 chalcogenides Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 32
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 32
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 18
- 239000002356 single layer Substances 0.000 description 17
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000005669 field effect Effects 0.000 description 6
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- 239000010703 silicon Substances 0.000 description 6
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- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000005530 etching Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- 239000004570 mortar (masonry) Substances 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021573 transition metal iodide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000011534 incubation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to the technical field of two-dimensional semiconductor materials, and provides a transition metal chalcogenide thin-layer material, and a preparation method and application thereof, wherein transition metal oxide and iodide salt are used as transition metal element sources, and the chalcogenide source and the transition metal element source are subjected to chemical vapor deposition reaction on a substrate in an atmosphere of protective gas, so that the transition metal chalcogenide thin-layer material with a crystal domain size of 10-600 mu m, a thickness of 0.7-20 nm and a defect concentration of not more than 1.5 multiplied by 10 can be prepared within one minute 12 Per cm 2 The nano-structure material has good appearance, good uniformity and excellent optical and electrical properties, and can be applied to the fields of micro-nano structure devices, optical devices, photoelectric devices, chemical biosensors or electrochemical catalysis and the like.
Description
Technical Field
The invention relates to the technical field of two-dimensional semiconductor materials, in particular to a transition metal chalcogenide thin-layer material and a preparation method and application thereof.
Background
The development of integrated circuits based on semiconductor silicon has greatly advanced modern information technology. Due to physical laws such as short channel effect and surface interface effect and the limitation of manufacturing cost of integrated circuits, mainstream Complementary Metal Oxide Semiconductor (CMOS) technology has reached a 5nm technology node, and continuation of moore's law faces termination or delay. The search for the next generation of semiconductor materials is one of the mainstream research and development directions in recent years in the scientific community and the industrial community, and electronic and photoelectric devices with higher integration level and more excellent performance are expected to be prepared.
Since single-layer graphene is prepared by a Geim research group at Manchester university in the United kingdom in 2004 through a mechanical stripping method, researchers find that a two-dimensional van der Waals layered material has an atomic-scale longitudinal dimension and a clean surface without dangling bonds, has unique physical properties such as high mobility and good mechanical properties, and further attracts extensive attention of the researchers. The transition metal chalcogenide (such as molybdenum disulfide, tungsten disulfide and the like) has the characteristics of excellent electrical property, photoelectric property, adjustable band gap (0.9-2 eV) and the like, and further has great potential in the fields of micro-nano structure devices, optical devices, photoelectric devices, chemical biosensors, electrochemical catalysis and the like. The defects such as crystal boundary and the like can cause scattering of current carriers to reduce mobility, so that the performance of a micro-nano structure device is influenced, and therefore, the preparation of a large-size and high-quality two-dimensional transition metal chalcogenide thin-layer material is one of the prerequisites for application.
Chemical vapor deposition is a common process in the silicon-based semiconductor industry and is also an important method for preparing two-dimensional transition metal chalcogenides. Taking molybdenum disulfide as an example, a traditional chemical vapor deposition method generally uses molybdenum trioxide powder and sulfur powder as precursors, and because the saturated vapor pressure of a molybdenum trioxide source is low and is difficult to volatilize effectively, and the melting point and the saturated vapor pressure of the molybdenum trioxide and the sulfur source are different greatly, the diffusion degrees of the molybdenum trioxide source and the sulfur source in a growth system are inconsistent, so that the obtained sample has poor uniformity, slow growth process and domain sizeSmall size and high defect concentration (greater than 10) 13 Per cm 2 ). In order to realize the second-level (the preparation time is controlled within one minute) and controllable preparation of the high-quality two-dimensional transition metal chalcogenide thin-layer material, researchers make various optimization attempts on the aspects of precursors, atmosphere, substrates and the like.
Chinese patent CN106811731A (published Japanese 2017.06.09) discloses a chemical vapor deposition method for preparing tungsten disulfide, which comprises the steps of taking tungsten trioxide powder and sulfur powder as precursors, placing the sulfur powder at the upstream, placing the tungsten trioxide powder in a quartz boat at the center of a heating zone of a tube furnace, and obliquely putting a silicon wafer on the quartz boat for chemical vapor deposition growth; the method can prepare the tungsten disulfide single-layer material, but the crystal domain size is small, the film is difficult to obtain, and the growth time is as long as 15-45 minutes. The prior art also discloses a chemical vapor deposition method for preparing large-size tungsten disulfide, which adopts gold as a substrate, and performs multi-step growth-etching through inert gas and hydrogen, so that the method improves the domain size of disulfide, but the prepared disulfide can be used for constructing a micro-nano structure device only by transferring to an insulating substrate, and in addition, the used gold substrate is expensive in price, and the preparation time is longer and reaches 300 minutes due to multi-step growth-etching circulation.
In summary, there still exist many problems in the preparation of the transition metal chalcogenide thin layer material, and there is a need to develop a preparation process with fast material growth rate, large domain size and good uniformity of the prepared transition metal chalcogenide thin layer material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The preparation method can improve the volatilization speed of the transition metal element so as to improve the growth rate of the material, the required heat preservation time is short, the transition metal chalcogenide thin-layer material with the crystal domain size of 10-600 mu m can be prepared within the time of no more than one minute, the thickness is 0.7-20 nm, the uniformity is good, the defect concentration is no more than 1.5 multiplied by 10 12 Per cm 2 。
In a first aspect of the invention, a method for preparing a transition metal chalcogenide thin layer material is provided.
Specifically, the preparation method of the transition metal chalcogenide thin-layer material comprises the following steps:
carrying out chemical vapor deposition reaction on a transition metal element source and a chalcogen element source on a substrate in an atmosphere of protective gas to prepare the transition metal chalcogen compound thin layer material; the transition metal element source includes: transition metal oxides and iodides.
The invention adopts transition metal oxide and iodine salt as transition metal element source, iodine element in the system forms volatile iodine simple substance in the reaction process, the iodine simple substance volatilizes rapidly, the volatilization of transition metal oxide in the system is driven, the supply amount of transition metal oxide in the system is increased, the reaction activity of transition metal oxide is improved, thereby the material grows rapidly, and the large-size transition metal chalcogenide thin layer material can be obtained in short reaction time.
Preferably, the mass ratio of the transition metal oxide to the iodine salt is 1 (0.1-2).
More preferably, the mass ratio of the transition metal oxide to the iodine salt is 1 (0.1-0.6).
Preferably, the ratio of the amounts of the transition metal element and the chalcogen element is 1 (10 to 300).
More preferably, the ratio of the amount of the transition metal element and the chalcogen element is 1:10, 1:20, 1:50, 1:100, 1:150, or 1: 300.
Preferably, the transition metal oxide is molybdenum trioxide and/or tungsten trioxide.
Preferably, the chalcogen source is one or more of a sulfur source, a selenium source and a tellurium source.
Preferably, the sulfur source is one or more of sulfur powder, selenium powder and tellurium powder.
Preferably, the iodide salt is potassium iodide.
Preferably, the pressure of the chemical vapor deposition reaction is 0.05 to 760 Torr.
More preferably, the pressure of the chemical vapor deposition reaction is 100 to 760 Torr.
Preferably, the chemical vapor deposition reaction is carried out in a tube furnace comprising a first heating zone and a second heating zone, the transition metal source being disposed in the first heating zone and the chalcogen source being disposed in the second heating zone.
Preferably, the second heating zone is located upstream of the first heating zone of the tube furnace.
Preferably, the method for preparing the transition metal chalcogenide thin layer material comprises the following steps:
placing the transition metal element source and the chalcogen element source on a substrate in a protective gas atmosphere, heating at a heating rate of 10-60 ℃/min, wherein the temperature of a first heating area is increased to 500-900 ℃, the temperature of a second heating area is increased to 100-200 ℃, then carrying out heat preservation at the temperature, the heat preservation time is 0-60 min, and cooling in the protective gas atmosphere after the reaction is finished.
Preferably, the heating rate is 30-40 ℃/min.
Preferably, the temperature of the first heating zone is raised to 700-850 ℃.
Preferably, the heat preservation time is 0-20 s.
Preferably, the protective gas is nitrogen and/or argon.
Preferably, the introduction rate of the protective gas is 1-1000 sccm.
More preferably, the introduction rate of the protective gas is 10 to 200 sccm.
Preferably, the cooling is to room temperature.
Preferably, the substrate is a silicon wafer and/or c-plane sapphire.
A second aspect of the invention provides a transition metal chalcogenide thin layer material.
The invention protects the transition metal chalcogenide thin-layer material prepared by the preparation method of the transition metal chalcogenide thin-layer material, and the crystal domain size of the transition metal chalcogenide thin-layer material is 10-600 mu m.
Preferably, the crystal domain size of the transition metal chalcogenide thin-layer material is 50-550 μm.
Preferably, the thickness of the transition metal chalcogenide thin layer material is 0.7-20 nm.
Preferably, the transition metal chalcogenide thin layer material is a molybdenum disulfide thin layer material or a tungsten disulfide thin layer material.
Preferably, the defect concentration of the molybdenum disulfide thin layer material does not exceed 1.5 x 10 12 Per cm 2 。
A third aspect of the invention provides a use of a transition metal chalcogenide thin layer material.
The invention protects the application of the transition metal chalcogenide thin-layer material in the fields of micro-nano structure devices, optical devices, photoelectric devices, chemical biosensors or electrochemical catalysis.
Preferably, the transition metal chalcogenide thin layer material is applied to the preparation of a field effect transistor.
Preferably, the mobility of the field effect transistor is not less than 175cm 2 V -1 s -1 On-off ratio of not less than 10 8 。
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method comprises the steps of taking transition metal oxide and iodide as transition metal element sources, carrying out chemical vapor deposition reaction on a substrate by using the chalcogen source and the transition metal element source in an atmosphere of protective gas, increasing the volatilization activity and the reaction activity of the transition metal oxide by using the iodide, increasing the volatilization speed of the transition metal element in a system, and increasing the supply amount of the transition metal element in the system, so that the growth rate of the material is increased, and the preparation method can prepare the transition metal chalcogen compound thin-layer material with the crystal domain size of 10-600 mu m within less than one minute;
(2) the crystal domain size of the transition metal chalcogenide thin-layer material prepared by the invention can reach 10-600Mum, thickness of 0.7-20 nm, and defect concentration not more than 1.5 × 10 12 Per cm 2 The crystal has high quality, good uniformity and good appearance, and has wide application prospect;
(3) the transition metal chalcogenide thin layer material prepared by the method has excellent optical and electrical properties, can be applied to the fields of micro-nano structure devices, optical devices, photoelectric devices, chemical biosensors or electrochemical catalysis and the like, and the mobility of the devices based on the transition metal chalcogenide thin layer material can reach 175cm 2 V -1 s -1 The on-off ratio can reach 10 8 The device has higher electrical quality and high reliability.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a transition metal chalcogenide thin layer material;
FIG. 2 is an optical microscope of a single-layer Mo disulfide material prepared in example 1 of the present invention;
FIG. 3 is a Raman spectrum of a single-layer molybdenum disulfide material prepared in example 1 of the present invention under a laser of 532 nm;
FIG. 4 is a scanning transmission microscope of a single-layer molybdenum disulfide material prepared in example 1 of the present invention;
FIG. 5 is a photoluminescence spectrum of a single-layer molybdenum disulfide material prepared in example 1 under a laser of 532 nm;
fig. 6 is an output characteristic curve and a transfer characteristic curve of a back gate field effect transistor device constructed by the molybdenum disulfide single-layer material prepared in embodiment 1 of the present invention;
FIG. 7 is an optical microscopic image and a Raman spectrum under 532nm laser of the molybdenum disulfide thin layer material prepared in example 2 of the present invention;
FIG. 8 is an optical microscope photograph of a thin layer of molybdenum disulfide material prepared in example 3 of the present invention;
FIG. 9 is an optical microscope photograph of a tungsten disulfide layer prepared in example 4 of the present invention;
FIG. 10 is an optical microscope photograph of a molybdenum disulfide layer material prepared in comparative example 1 of the present invention;
FIG. 11 is an optical microscope photograph of a thin layer of molybdenum disulfide material prepared in comparative example 2 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A preparation method of a molybdenum disulfide single-layer material comprises the following steps:
(1) uniformly mixing 10mg of molybdenum trioxide and 1mg of potassium iodide in a mortar to prepare a transition metal element source;
(2) placing 3mg of transition metal element source in a quartz boat, placing the silicon wafer face down above the transition metal element source in the quartz boat, and placing the quartz boat in a first heating zone of a tube furnace; placing the quartz boat filled with 100mg of sulfur powder in a second heating zone upstream of the first heating zone;
(3) introducing 100sccm argon for 20 minutes, exhausting air in the tubular furnace, heating the first heating area to 790 ℃ at the speed of 40 ℃/min, heating the second heating area to 150 ℃, keeping the temperature for 2s, stopping heating, and naturally cooling to room temperature to obtain the molybdenum disulfide single-layer material; the above preparation process is as shown in fig. 1, under the protective gas atmosphere, the substrate is placed above the transition metal element source (transition metal oxide and potassium iodide), and the transition metal element source and the chalcogen element source are subjected to chemical vapor deposition reaction together to prepare the transition metal chalcogen compound thin layer material.
As shown in FIG. 2, the domain size of the single-layer material of molybdenum disulfide prepared in example 1 of the present invention is 550 μm.
As can be seen from FIG. 3, in the Raman spectrum of the molybdenum disulfide single-layer material prepared in example 1 of the present invention under the laser of 532nm, the distance between two peaks is 20.7cm -1 The material is shown to be a monolayer of molybdenum disulfide.
As can be seen from the figure 4, it is,the defect concentration of the molybdenum disulfide single-layer material prepared in the embodiment 1 of the invention is only 1.5 multiplied by 10 12 Per cm 2 The material is shown to have higher crystal quality.
As can be seen from fig. 5, the molybdenum disulfide single-layer material prepared in example 1 of the present invention has a direct band gap, the band gap is 1.8eV, and exhibits a better light emitting property.
Application example
A field effect transistor is manufactured by adopting the molybdenum disulfide single-layer material in embodiment 1 of the invention.
Fig. 6a and fig. 6b are an output characteristic curve and a transfer characteristic curve of a back gate field effect transistor device constructed by a molybdenum disulfide single-layer material obtained in embodiment 1 of the present invention, respectively; as can be seen from FIGS. 6a and 6b, the mobility of the field effect transistor of the single-layer molybdenum disulfide material prepared in example 1 of the present invention reaches 175cm 2 V -1 s -1 On/off ratio of 10 8 The device has higher electrical quality and high reliability.
Example 2
The preparation method of the molybdenum disulfide thin layer material is different from the embodiment 1 in that the substrate used in the step (1) is c-plane sapphire, and the rest is the same as the embodiment 1.
FIG. 7a and FIG. 7b are an optical microscope image and a Raman spectrum under 532nm laser of the molybdenum disulfide thin layer material prepared in example 2 of the present invention, respectively; as can be seen from FIG. 7a and FIG. 7b, the domain size of the molybdenum disulfide thin layer material prepared in example 2 of the present invention is 244 μm and the morphology is good.
Example 3
The preparation method of the molybdenum disulfide thin layer material is different from the embodiment 1 in that the heat preservation time in the step (3) is 10s, and the rest is the same as the embodiment 1.
As can be seen from FIG. 8, the thin layer of molybdenum disulfide material prepared in example 3 of the present invention can be continuously and uniformly coated on the substrate.
Example 4
A preparation method of a tungsten disulfide thin layer material comprises the following steps:
(1) uniformly mixing 10mg of tungsten trioxide and 1mg of potassium iodide in a mortar to prepare a transition metal element source;
(2) placing 3mg of transition metal element source in a quartz boat, placing the quartz boat above the transition metal element source in the quartz boat with the silicon wafer facing downwards, placing the quartz boat in a first heating zone of a tube furnace, and placing the quartz boat filled with 100mg of sulfur powder in a second heating zone at the upstream of the first heating zone;
(3) and introducing 100sccm argon for 20 minutes to exhaust the air in the tubular furnace, heating the first heating area to 850 ℃ at the speed of 40 ℃/min, heating the second heating area to 150 ℃, keeping the temperature for 2 seconds, stopping heating, and naturally cooling to room temperature to obtain the tungsten disulfide thin layer material.
As can be seen from fig. 9, the domain size of the tungsten disulfide thin layer material prepared in embodiment 4 of the present invention reaches 50 μm, and the morphology is good, which proves that the tungsten disulfide thin layer material with a larger domain size can be prepared in the second-order (2s) heat preservation time by the preparation method of the present invention.
Comparative example 1
A method for preparing a molybdenum disulfide thin layer material is different from the method in the embodiment 1 in that a transition metal source used in the step (1) does not contain potassium iodide, only molybdenum trioxide is used, the temperature preservation time in the step (3) is prolonged to 20 minutes, and the rest is the same as the method in the embodiment 1.
As can be seen from fig. 10, the crystal domain size of the molybdenum disulfide thin layer material prepared in comparative example 1 is 15 μm, and although the incubation time is prolonged in comparative example 1, the crystal domain size of the material is small due to the slow growth rate of the material, because the molybdenum trioxide has a high melting point and a small volatilization amount during the chemical vapor deposition process, that is, the transition metal element is supplied in a small amount during the growth of the material, so that the growth rate of the prepared material is slow and the crystal domain size is small.
Comparative example 2
A preparation method of a molybdenum disulfide thin layer material is different from that of the embodiment 1 in that potassium iodide in a transition metal element source used in the step (1) is replaced by sodium chloride, the temperature preservation time in the step (3) is prolonged to 2 minutes, and the rest is the same as that of the embodiment 1.
As shown in fig. 11, the domain size of the molybdenum disulfide thin layer material prepared in comparative example 2 is 100 μm, which illustrates that the domain size of the molybdenum disulfide thin layer material prepared in comparative example 2 is larger than that of comparative example 1, but the required time is correspondingly prolonged, the efficiency is low, and the domain size of the material of comparative example 2 is significantly lower than that of example 1 of the present invention.
In summary, the invention adopts the transition metal oxide and the iodide salt as the transition metal element source, and the chalcogen element source and the transition metal element source are subjected to chemical vapor deposition reaction on the substrate in the atmosphere of protective gas, so that the preparation of the transition metal chalcogenide thin-layer material on different substrates can be realized, the preparation time is not more than one minute and even can reach the second level, the domain size of the prepared thin-film material can reach 10-600 μm, and the thickness is 0.7-20 nm.
Claims (10)
1. A method for preparing a transition metal chalcogenide thin layer material is characterized by comprising the following steps:
carrying out chemical vapor deposition reaction on a transition metal element source and a chalcogen element source on a substrate in an atmosphere of protective gas to prepare the transition metal chalcogen compound thin layer material;
the transition metal element source includes: transition metal oxides and iodonium salts.
2. The preparation method according to claim 1, wherein the mass ratio of the transition metal oxide to the iodine salt is 1 (0.1-2).
3. The method according to claim 1, wherein the ratio of the amounts of the transition metal in the transition metal element source and the chalcogen in the chalcogen source is 1 (10 to 300).
4. The production method according to claim 1, wherein the transition metal oxide is molybdenum trioxide and/or tungsten trioxide.
5. The preparation method according to claim 1, wherein the chalcogen source is one or more of a sulfur source, a selenium source and a tellurium source.
6. The method of claim 1, wherein the chemical vapor deposition reaction is performed in a tube furnace, the tube furnace comprising a first heating zone and a second heating zone, the transition metal source being disposed in the first heating zone and the chalcogen source being disposed in the second heating zone.
7. The method of claim 6, comprising the steps of:
placing the transition metal element source and the chalcogen element source on a substrate in a protective gas atmosphere, heating at a heating rate of 10-60 ℃/min, wherein the temperature of a first heating area is increased to 500-900 ℃, the temperature of a second heating area is increased to 100-200 ℃, then carrying out heat preservation at the temperature, the heat preservation time is 0-60 min, and cooling in the protective gas atmosphere after the reaction is finished.
8. The transition metal chalcogenide thin-layer material prepared by the preparation method according to any one of claims 1 to 7, wherein the domain size of the transition metal chalcogenide thin-layer material is 10 to 600 μm.
9. The thin transition metal chalcogenide material according to claim 8, wherein the thin transition metal chalcogenide material has a thickness of 0.7 to 20 nm.
10. Use of a transition metal chalcogenide thin layer material according to claim 8 or 9 in the fields of micro-nano structure devices, optical devices, photovoltaic devices, chemical biosensors or electrochemical catalysis.
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