CN110808281A - Single-layer MoS2-WS2Method for preparing transverse heterojunction - Google Patents
Single-layer MoS2-WS2Method for preparing transverse heterojunction Download PDFInfo
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 10
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
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- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/22—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds
- H01L29/221—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds including two or more compounds, e.g. alloys
- H01L29/225—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIBVI compounds including two or more compounds, e.g. alloys in different semiconductor regions, e.g. heterojunctions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
- H01L29/0684—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape, relative sizes or dispositions of the semiconductor regions or junctions between the regions
Abstract
Single-layer MoS2‑WS2A preparation method of a transverse heterojunction belongs to the field of nano material growth. And carrying out electrochemical oxidation treatment on the selected precursor source to realize volatilization of the precursor source corresponding to the molybdenum and the tungsten at different temperatures, and preparing the transverse heterojunction with the micron-sized clear interface in one step by a chemical vapor deposition method. The method for growing the transverse heterojunction is to use inert gas as transport gas of reaction sources (a molybdenum source, a tungsten source and a sulfur source) in a tubular furnace with accurate temperature control and control different chemical vapor deposition reactions to form the transverse heterojunction. Single-layer MoS prepared by the invention2‑WS2The transverse heterojunction has micron-sized clear heterojunction boundary, and the transverse dimension can reach more than one hundred microns. The method has controllable growth processThe growth temperature window can be effectively widened, the growth temperature is reduced, and the controllable growth of the size and the interface is realized.
Description
Technical Field
The invention belongs to the field of nano material growth, and relates to preparation of a two-dimensional transition metal chalcogenide heterojunction.
Technical Field
In 2004, professor Geim and Novoseov used a tape mechanical stripping method to prepare single-layer graphene, thereby opening the door in the field of Two-dimensional Materials. Graphene is an ideal two-dimensional crystal composed of a single layer of carbon atoms, and has an electron mobility μ of 2 × 105cm2·V-1·s-1The thermal conductivity kappa is about 5000W/mK higher than that of diamond and graphite, the elastic modulus E is 1.0TPa, and the strength sigma isint130GPa, the method has wide application prospect in the construction field of future micro-nano devices. However, graphene is very limited in practical application as a zero band gap material. With molybdenum sulphide (MoS)2) And tungsten sulfide (WS)2) The transition Metal sulfides (transition Metal Dichalcogenides) have band gaps (1.3-2.0eV) which are increased along with the reduction of the number of layers, are indirect band gap semiconductors in bulk and multilayer, are converted into direct band gap semiconductors in single layer, have remarkably improved photoelectric conversion efficiency, and have the band gaps as high as 500-1000cm2·V-1·s-1The theory of (2) predicting the carrier mobility has great application potential in the field of photoelectric information, and is favored by researchers.
Because the performance of a single two-dimensional material is single, and the wide application requirements are difficult to meet, a plurality of two-dimensional materials can be utilized to construct a plurality of heterostructures of different types, so that multifunctional application is realized, and meanwhile, the two-dimensional heterostructures have great theoretical research value in the fields of semiconductors and condensed state physics.
Two-dimensional material heterojunction mainly divide into perpendicular heterojunction and horizontal heterojunction, and theory and experimental study are mostly concentrated on perpendicular two-dimensional heterojunction at present stage, and horizontal heterojunction is because to the requirement height of heterogeneous material lattice matching degree, and experimental conditions is strict, and difficult acquisition high quality sample, consequently to the physical properties research work and the device application of horizontal heterojunction equidirectional photoelectricity relatively less. The two-dimensional material vertical heterojunction is mostly prepared by a simpler mechanical stripping transfer assembly method, and is a novel van der waals contact mode. Meanwhile, the two-dimensional vertical heterojunction exhibits a novel physicochemical phenomenon, so that its properties have been widely studied. However, the horizontal heterojunction has a complex manufacturing process and harsh conditions, and the research work is slow. The current preparation method of the two-dimensional transverse heterojunction is mainly a chemical vapor deposition method, the process is generally divided into single-step synthesis and multi-step synthesis, and a small amount of two-dimensional transverse heterojunction, mainly a transverse heterojunction of a transition metal sulfide series, is prepared at present. However, in the prepared transverse heterojunction, a wider alloy area appears at the interface, and the performance of the heterojunction is seriously influenced by serious interface amorphization. Thus, there are still many problems to be solved in the fabrication of two-dimensional lateral heterojunctions. The two-dimensional material transverse heterojunction is used as a semiconductor heterojunction with atomic-scale thickness, and has great research significance and application prospect in the aspect of realizing electronic devices with atomic-scale thickness.
Disclosure of Invention
The invention provides a single-layer MoS2-WS2A method for fabricating a lateral heterojunction.
The technical scheme of the invention is as follows: single-layer MoS2-WS2The preparation method of the transverse heterojunction is characterized in that precursors of Mo source oxide or/and W source oxide are prepared or/and processed, so that the volatilization temperatures of the two precursors have difference, and therefore, the temperature regulation and control in the chemical vapor deposition process are realized, namely when the volatilization of the first metal source is finished, the volatilization process of the second metal source is started, the growth processes of the two materials can be separated and volatilized and grown step by step at different temperatures, and the transverse heterojunction with a micron-sized clear interface is prepared by a growth and vulcanization one-step method.
The method specifically comprises the following steps:
① preparation of molybdenum source oxide precursor, oxidizing molybdenum foil by electrochemical workstation oxidation to obtain MoOxA Mo foil;
② preparing precursor of tungsten source oxide, mechanically grinding and mixing tungsten oxide powder and inorganic sodium salt according to a certain molar ratio by using a mortar;
③ transferring tungsten source prepared by mixing tungsten oxide powder and sodium salt to the center of corundum boat, and adding MoOxthe/Mo foil is placed 1-2cm beside a tungsten source in the corundum boat, the growth substrate is placed or erected above the center of the corundum boat, the lower surface of the substrate is parallel to the opening of the corundum boat, a gap is formed between the lower surface of the substrate and the opening of the corundum boat, the smooth surface of the substrate faces downwards and is used for growing a transverse heterojunction on the surface of the substrate, and then the corundum boat is placed in a central high-temperature area of the tubular furnace; then, placing the other corundum boat filled with the sulfur powder in a low-temperature area with the upstream position of the carrier gas flow at the temperature range of 100-200 ℃, wherein the carrier gas flow enters from one end of the tubular furnace and exits from the other end;
④ in the chemical vapor deposition process, inert gas is introduced as carrier gas flow, the tubular furnace is first gas replaced to make the inside of the tubular furnace pure inert gas, then the gas flow is adjusted to carry out the reaction, the temperature of the center of the tubular furnace in the reaction is set according to time period, the temperature is divided into four stages, the first stage is the process of removing the combined water, the second stage is the process of molybdenum sulfide growth, the third stage is the process of tungsten sulfide growth, and the fourth stage is the natural cooling process.
Wherein, in the electrochemical oxidation in the step ①, the electrolyte comprises 0.1-0.5mol/L sodium fluoride and 0.1-0.5mol/L oxalic acid, the oxidation voltage is 3-5V, the oxidation current is-0.010-0.030A, and the oxidation time is 500-1000 s.
Preferably, the tungsten oxide powder and the sodium salt are mixed and ground in the step ② according to the molar ratio of 10:1-3: 1.
Among them, preferred is MoO in step ③xPositional relationship of Mo foil with tungsten oxide powder and sodium salt powder, MoOxthe/Mo foil is placed in the corundum boat at the rear end of the tungsten source, namely, relative to the downstream position in the flow direction of the carrier gas.
Preferably, in the step ④, the furnace tube is replaced and cleaned by using a flow of 300-500sccm, the reaction is performed by using a flow of 100-300sccm as a carrier gas, the first stage is to heat the furnace tube from room temperature to 200 ℃ at a heating rate of 20-50 ℃/min, keep the temperature for 10-60min, then heat the furnace tube to 700 ℃ at a heating rate of 20-50 ℃/min, keep the temperature for 1-15min, then heat the furnace tube to 950 ℃ at a heating rate of 30-50 ℃/min, keep the temperature for 1-15min, and finally naturally cool the furnace tube to room temperature under the protection of an inert gas.
The sodium salt is sodium sulfate, sodium chloride, sodium nitrate and the like.
The growth substrate may be selected from: silicon dioxide/silicon wafer, sapphire, quartz, mica, noble metals, etc.
Compared with the prior art, the invention has the advantages that:
the preparation method of the planar heterojunction of the two-dimensional material comprises the steps of carrying out electrochemical oxidation treatment on a selected precursor source and introducing sodium salt for auxiliary growth, so that the volatilization temperatures of the two precursors are obviously different, the growth processes of the two materials can be separated through temperature regulation, and the transverse heterojunction with a micron-sized clear interface is prepared in one step through a chemical vapor deposition method;
the preparation method of the two-dimensional material planar heterojunction provided by the invention can be used for preparing a transverse heterojunction with the size of 128 microns and can be used for performance research in the aspects of photoelectromagnetism and the like; the silicon dioxide/silicon wafer is used as a growth substrate, and the existing mature semiconductor processing technology is compatible, so that large-scale production can be realized; the method is also suitable for surface growth of sapphire, quartz, mica, noble metals and the like;
the preparation method of the two-dimensional material planar heterojunction is simple and high in controllability, and provides a new idea for preparation work of the two-dimensional material transverse heterojunction.
Drawings
FIG. 1 preparation of MoS in the examples2-WS2A simplified diagram of a molybdenum oxide source preparation device of a transverse heterojunction;
FIG. 2 illustrates the preparation of single-layer MoS according to the present invention2-WS2A schematic diagram of a chemical vapor deposition apparatus for a lateral heterojunction;
FIG. 3 is the MoS prepared in the example2-WS2Optical microscopy of a lateral heterojunction;
FIG. 4 shows MoS prepared in example2-WS2Atomic force microscopy of a lateral heterojunction; the arrow in the left figure points in the scanning direction of the scanning probe;
FIG. 5 is the MoS prepared in the example2-WS2A test pattern of a lateral heterojunction;
wherein (a) and (b) are optical microscope photographs, wherein ABC three points in (b) are photoluminescence at different positions in (c) and (d) and the positions (c) and (d) of Raman single-point test are single-point and image surface scanning imaging photoluminescence spectrums respectively; (e) and (f) are single-point and image surface scanning imaging Raman imaging images respectively. (Note: Junction represents a lateral heterojunction Junction region, 2LA (M) in a Raman spectrogram represents a secondary characteristic vibration peak of WS2, and A1g represents an interlayer characteristic vibration peak of MoS2 and WS 2).
Detailed Description
The present invention will be further described with reference to the following detailed embodiments and the accompanying drawings, but the present invention is not limited to the following.
Example 1
Single-layer MoS2-WS2The preparation method of the transverse heterojunction comprises the following steps:
in this experiment, SiO with a thickness of 400 μm was used2(wherein SiO)2300nm) as a growth substrate, first cutting a 4 inch silicon wafer into square substrates of 1cm × 1 cm; and secondly, carrying out ultrasonic cleaning on the cut silicon wafer for 20min according to the sequence of acetone, alcohol and deionized water, setting the power at 70W, and cleaning the surface of the silicon wafer.
Preparing a molybdenum source precursor: preparing electrolyte, namely weighing oxalic acid and sodium fluoride respectively by using an electronic balance, putting 9.45g and 0.21g of oxalic acid and sodium fluoride respectively into a beaker, stirring and dissolving, adding deionized water to dissolve, pouring into a volumetric flask, and fixing the volume to 500 ml; cutting a molybdenum foil with the purity of 99.99% into the size of 1x 1 cm; electrochemical oxidation, and preparing MoO by oxidation treatment of molybdenum foil by using electrochemical workstationxThe oxidation voltage of the/Mo foil sample is 4V, the oxidation current is-0.020A, and the oxidation time is 700 s. (see the attached figure 1 for details)
Preparing a tungsten source precursor, namely grinding and mixing nano tungsten oxide powder with the purity of 99.99% and anhydrous sodium sulfate powder with the purity of 99.99% according to the molar ratio of 5: 1.
Transferring 30mg of tungsten source prepared by mixing tungsten oxide powder and sodium sulfate, and oxidizing MoOxCutting the/Mo foil into proper sizes, respectively placing the cut pieces on two sides of the center of the corundum boat, placing the growth substrate above the center of the corundum boat with the smooth oxide layer facing downwards, and then placing the corundum boat in a central high-temperature area of a tube furnace. (see FIG. 2 for details)
Weighing 2g of high-purity sulfur with the purity of 99.9 percent, placing the high-purity sulfur in a corundum boat, placing the boat at the upstream of the molybdenum source and the tungsten source in the direction of carrier gas in a quartz tube, heating the high-purity sulfur to 180 ℃ by using a heating belt at the heating rate of 30 ℃/min when the temperature of a furnace central temperature zone reaches 500 ℃, then preserving the temperature until the temperature in the furnace is cooled to 400 ℃, and removing the heating belt. (see FIG. 2 for details)
The central temperature zone of the tubular furnace is divided into four stages, the first stage removes the bound water in the sample, the heating rate is 20 ℃/min, the temperature is raised to 200 ℃, and the temperature is preserved for 20 min; in the second stage, the growth of molybdenum sulfide is controlled, the temperature rise rate is 30 ℃/min, the temperature is raised to 700 ℃, and the temperature is kept for 5 min; controlling the growth of tungsten sulfide in the third stage, raising the temperature to 850 ℃ at the rate of 30 ℃/min, and keeping the temperature for 10 min; the fourth stage is set to a natural cooling process.
Inert gas argon is selected as carrier gas, before the temperature rise is started, large-flow argon (300sccm) is introduced, the air in the quartz tube is discharged, and the exhaust time is 30 min.
After the exhaust is finished, the temperature rise process is started according to a preset temperature rise curve, the flow rate of the argon is reduced and adjusted to be 100sccm until the experiment is finished.
After the reaction is finished, the sample is naturally cooled to room temperature along with the furnace in the argon atmosphere, the sample is taken out to be tested and analyzed by characterization means such as an optical microscope, a scanning electron microscope, an atomic force microscope, a Raman spectrum and the like, and the details are shown in an attached figure 3-5.
Claims (7)
1. Single-layer MoS2-WS2Method for producing a lateral heterojunction, characterized in thatThe precursors of the Mo source oxide or/and the W source oxide are treated to ensure that the volatilization temperatures of the two precursors have difference, so that the growth process of the two materials can be separated and volatilized at different temperatures step by regulating and controlling the temperature in the chemical vapor deposition process, namely when the volatilization of the first metal source is finished, the volatilization process of the second metal source is started, and the transverse heterojunction with a micron-sized clear interface is prepared by a one-step growth and vulcanization method.
2. A single layer MoS according to claim 12-WS2The preparation method of the transverse heterojunction is characterized by comprising the following steps:
① preparation of molybdenum source oxide precursor, oxidizing molybdenum foil by electrochemical workstation oxidation to obtain MoOxA Mo foil;
② preparing precursor of tungsten source oxide, mechanically grinding and mixing tungsten oxide powder and inorganic sodium salt according to a certain molar ratio by using a mortar;
③ transferring tungsten source prepared by mixing tungsten oxide powder and sodium salt to the center of corundum boat, and adding MoOxthe/Mo foil is placed 1-2cm beside a tungsten source in the corundum boat, the growth substrate is placed or erected above the center of the corundum boat, the lower surface of the substrate is parallel to the opening of the corundum boat, a gap is formed between the lower surface of the substrate and the opening of the corundum boat, the smooth surface of the substrate faces downwards and is used for growing a transverse heterojunction on the surface of the substrate, and then the corundum boat is placed in a central high-temperature area of the tubular furnace; then, placing the other corundum boat filled with the sulfur powder in a low-temperature area with the upstream position of the carrier gas flow at the temperature range of 100-200 ℃, wherein the carrier gas flow enters from one end of the tubular furnace and exits from the other end;
④ in the chemical vapor deposition process, inert gas is introduced as carrier gas flow, the tubular furnace is first gas replaced to make the inside of the tubular furnace pure inert gas, then the gas flow is adjusted to carry out the reaction, the temperature of the center of the tubular furnace in the reaction is set according to time period, the temperature is divided into four stages, the first stage is the process of removing the combined water, the second stage is the process of molybdenum sulfide growth, the third stage is the process of tungsten sulfide growth, and the fourth stage is the natural cooling process.
3. A single layer MoS according to claim 12-WS2The preparation method of the transverse heterojunction is characterized in that during the electrochemical oxidation in the step ①, the electrolyte comprises 0.1-0.5mol/L of sodium fluoride and 0.1-0.5mol/L of oxalic acid, the oxidation voltage is 3-5V, the oxidation current is-0.010-0.030A, and the oxidation time is 500-1000 s.
4. A single layer MoS according to claim 12-WS2The method for producing a lateral heterojunction is characterized in that in step ②, tungsten oxide powder and a sodium salt are mixed and ground in a molar ratio of 10:1 to 3: 1.
5. A single layer MoS according to claim 12-WS2Method for the preparation of a lateral heterojunction, characterized in that MoO is used in step ③xPositional relationship of Mo foil with tungsten oxide powder and sodium salt powder, MoOxthe/Mo foil is placed in the corundum boat at the rear end of the tungsten source, namely, relative to the downstream position in the flow direction of the carrier gas.
6. A single layer MoS according to claim 12-WS2The preparation method of the transverse heterojunction is characterized in that in step ④, 500sccm gas flow of 300-plus-500 sccm is adopted for replacing and cleaning a furnace tube, 300sccm gas flow of 100-plus-300 sccm is adopted as a carrier gas for reaction, the temperature rise rate is controlled to be 20-50 ℃/min in the first stage, the furnace temperature of the tubular furnace is raised from room temperature to 150-plus-200 ℃, the temperature is kept for 10-60min, then the furnace temperature is raised to 600-plus-700 ℃ at the temperature rise rate of 20-50 ℃/min, the temperature is kept for 1-15min, then the furnace temperature is raised to 850-plus-950 ℃ at the temperature rise rate of 30-50 ℃/min, the temperature is kept for 1-15min, and finally the temperature of the tubular furnace is naturally lowered to.
7. A single layer MoS according to claim 12-WS2The preparation method of the transverse heterojunction is characterized in that the sodium salt is selected from sodium sulfate, sodium chloride and sodium nitrate.
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