CN116835651A - Controllable preparation method of high-length-width-ratio molybdenum disulfide nano-belt or micro-belt - Google Patents
Controllable preparation method of high-length-width-ratio molybdenum disulfide nano-belt or micro-belt Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 85
- 239000002127 nanobelt Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 150
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 18
- 238000004528 spin coating Methods 0.000 claims description 18
- 239000002356 single layer Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000543 intermediate Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PHXYUNOGCCMYBD-UHFFFAOYSA-N [O].[Na].[Mo] Chemical compound [O].[Na].[Mo] PHXYUNOGCCMYBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000002074 nanoribbon Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 6
- 239000010980 sapphire Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002365 multiple layer Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/12—Production of homogeneous polycrystalline material with defined structure directly from the gas state
- C30B28/14—Production of homogeneous polycrystalline material with defined structure directly from the gas state by chemical reaction of reactive gases
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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Abstract
The invention relates to a controllable preparation method of a high-aspect-ratio molybdenum disulfide nanobelt or a micron belt, belonging to the field of low-dimensional material preparation. Using molybdate solution as a molybdenum source, using sodium hydroxide solution as a catalyst, using sulfur powder as a sulfur source, and obtaining the catalyst through a chemical vapor deposition method; by adjusting different proportions of the sodium molybdate and the sodium hydroxide mixed solution, the controllable adjustment of the size and the orientation of the nanometer/micrometer band can be realized; the adjustment of the number of nano/micron band layers can be realized by adjusting the growth time; finally, the molybdenum disulfide nanometer/micrometer bands with different sizes, orientations and layers and with the length-width ratio larger than 100 can be controllably obtained on the substrate. The preparation process is simple, the production cost is low, the size, the orientation and the layer number are controllable, and the preparation process is suitable for batch production.
Description
Technical Field
The invention belongs to the field of low-dimensional material preparation, and particularly relates to a controllable preparation method of a high-aspect-ratio molybdenum disulfide nanobelt or micrometer belt.
Background
Molybdenum disulfide (MoS) 2 ) The organic light-emitting diode has excellent mechanical, electrical and photoelectric characteristics, and has great application potential in the aspects of ultrathin electronic, photoelectric, sensing and storage devices and the like. Especially when its morphology is altered or further reduced to quasi-one dimension (nano/micro bands) will exhibit the following: metallic edge states, one-dimensionally limited electrical and magnetic properties, and more novel properties such as more excellent optoelectronic properties. Currently, for low-dimensional MoS 2 The research of the nanometer/micrometer band is still based on theoretical calculation, and the experimental preparation of the nanometer/micrometer band with high aspect ratio is still difficult. But there are few current methods for preparing low-dimensional MoS 2 The nano/micron band is mainly realized by etching from top to bottom through micro-nano manufacturing technology. However, this method is complicated in steps and inevitably introduces impurities and defects, which affect the crystal quality of the obtained material. Compared with the top-down method, the Chemical Vapor Deposition (CVD) method is relatively simple and low in cost, but the CVD method is adopted at present to obtain the uniform-distribution MoS with controllable orientation, size and layer number and high aspect ratio 2 Nano/micro bands still present significant challenges.
Disclosure of Invention
The invention provides a controllable preparation method of a molybdenum disulfide nano/micron belt with a high length-width ratio, which is characterized in that a molybdate solution is used as a molybdenum source, a sodium hydroxide solution is used as a catalyst, sulfur powder is used as a sulfur source, and the molybdenum disulfide nano/micron belt is obtained by a tube furnace chemical vapor deposition method; by adjusting the concentration of sodium hydroxide, the controllable adjustment of the size and orientation of the nanometer/micrometer band can be realized; the adjustment of the number of nano/micron band layers can be realized by adjusting the growth time; finally, the high aspect ratio molybdenum disulfide nanometer/micrometer bands with different sizes, orientations and layers are controllably obtained on the substrate; the method solves the technical problems that impurities and defects are inevitably introduced in the preparation of nano/micron belts in the prior art, and the crystal quality of the obtained material is affected.
According to a first aspect of the present invention, there is provided a controllable preparation method of molybdenum disulphide nanoribbons or microribbons, comprising the steps of:
(1) Spin-coating a mixed solution of a molybdenum source and sodium hydroxide serving as a catalyst on a substrate to obtain a substrate uniformly distributed with the molybdenum source and the catalyst, wherein the molybdenum source is sodium molybdate or ammonium molybdate;
(2) Placing the substrate obtained in the step (1) in a third temperature zone of a three-temperature-zone chemical vapor deposition device, and placing sulfur powder in a first temperature zone, wherein the third temperature zone and the first temperature zone are separated by a second temperature zone; vacuumizing the three-temperature-zone chemical vapor deposition device, and then washing gas to enable air flow to blow from the direction of the first temperature zone to the direction of the third temperature zone; and then heating to sublimate the sulfur powder in the first temperature zone into a gaseous state, generating a sodium molybdenum oxide intermediate by the spin-coating on the substrate in the third temperature zone, and reacting the gaseous sulfur with the sodium molybdenum oxide intermediate to obtain the molybdenum disulfide nanobelt or the molybdenum disulfide micrometer belt.
Preferably, when the concentration of sodium hydroxide in the mixed solution is 1mM, six-fold symmetrical oriented growth nanoribbons are obtained;
when the concentration of sodium hydroxide in the mixed solution is more than 1mM and less than 1.5mM, six-fold symmetrically oriented grown nanobelts and double-fold symmetrically oriented grown micrometer belts are obtained;
when the concentration of sodium hydroxide in the mixed solution was 1.5mM, a micrometer band oriented in double symmetry was obtained;
when the concentration of sodium hydroxide in the mixed solution is more than 1.5mM and less than 5mM, a micrometer band oriented in double symmetry and a network micrometer band grown in disorder are obtained;
when the concentration of sodium hydroxide in the mixed solution is 5mM or more and 7mM or less, a network-like micro-strip grown in disorder is obtained.
Preferably, in the step (2), when the growth time is less than or equal to 5min, a single-layer molybdenum disulfide nanobelt or a single-layer molybdenum disulfide micrometer belt is obtained; when the growing time is more than 5min and less than 10min, the molybdenum disulfide nanobelts or micrometer belts containing single layers and multiple layers are obtained; when the growing time is more than or equal to 10min, the multi-layer molybdenum disulfide nano-belt or micro-belt is obtained.
Preferably, the reaction temperature of the first temperature zone is 150-250 ℃, the reaction temperature of the second temperature zone is 300-400 ℃, and the reaction temperature of the third temperature zone is 700-850 ℃.
Preferably, in the step (2), the substrate is placed in a third temperature zone of a three-temperature zone chemical vapor deposition device in a face-down manner, so that sodium-molybdenum-oxygen intermediates are more beneficial to flow on the surface of the substrate in the growth process.
Preferably, in the step (1), the spin coating is performed at a rotation speed of 1000rpm to 3000rpm for 60 seconds or longer.
Preferably, the aspect ratio of the molybdenum disulfide nanobelt or the molybdenum disulfide micrometer belt is more than 100.
Preferably, the substrate is subjected to an oxygen plasma treatment prior to spin coating.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The molybdenum disulfide nano/micron belt obtained by the invention has good crystal quality and high length-width ratio, can be more than 100, and is at a higher level than the molybdenum disulfide nano/micron belt obtained by the prior method.
(2) The method adopts a mode of pre-spin coating reactant solution on the substrate, and effectively improves the infiltration property of the solution and the substrate through oxygen plasma treatment. Compared with the mode of adopting reactant powder, the method is more beneficial to obtaining the molybdenum disulfide nanometer/micrometer band with better uniformity on the substrate.
(3) The method can realize the adjustment of the size and orientation of the molybdenum disulfide nanometer/micrometer band obtained by growth by adjusting the concentration of sodium hydroxide in the mixed solution of sodium molybdate and sodium hydroxide. The present method provides a higher controllability of the size and orientation of the obtained material than previous growth modes.
(4) The method can realize the adjustment of the number of layers of the grown molybdenum disulfide nano/micron belt by simply adjusting the reaction time, and has higher layer number controllability compared with the prior growth mode.
(5) The invention adopts the sapphire substrate with low cost, and does not need a special substrate with high cost; and the direct chemical vapor deposition of the molybdenum disulfide nano/micron belt is realized, and pollution and defects introduced in etching by a complicated and high-cost micro-nano processing technology are effectively avoided.
Drawings
Fig. 1 and 2 are characterization graphs of the resulting high aspect ratio molybdenum disulfide nano/micro ribbons, wherein: fig. 1 is a scanning electron micrograph, and fig. 2 is an X-ray photoelectron spectroscopy.
Fig. 3 is a schematic diagram of a preparation process, in which: fig. 3 (a) is a schematic diagram of a solution mixture of sodium molybdate and sodium hydroxide, which is added dropwise and spin-coated, and fig. 3 (b) is a schematic diagram of a chemical vapor deposition system.
Fig. 4 is an effect of sodium hydroxide concentration on the size and orientation of molybdenum disulfide nano/micro bands, wherein: the (a) in FIG. 4, the (b) in FIG. 4, and the (c) in FIG. 4 are optical micrographs of molybdenum disulfide nano/micro bands at sodium hydroxide concentrations of 1mM, 1.5mM, and 5mM, respectively.
Fig. 5 is a graph showing the effect of growth time on the number of layers of molybdenum disulfide nanoribbon/microband, wherein: the optical micrograph of the molybdenum disulfide nano/micro band was obtained in fig. 5 (a) and fig. 5 (b) at growth times of 5min and 10min, respectively.
Fig. 6 is an electrical and optoelectronic performance of a phototransistor prepared based on the molybdenum disulfide nanoribbon/microband, wherein: fig. 6 (a) is a transfer characteristic diagram thereof, and fig. 6 (b) is a plot of responsivity and specific detection rate thereof as a function of incident light power.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a high-aspect-ratio molybdenum disulfide nano/micron belt and a controllable preparation method thereof, which can realize controllable growth of molybdenum disulfide nano/micron belts with different sizes, orientations and layers on a sapphire substrate. In actual preparation, according to the requirements of the designed target material, the high aspect ratio molybdenum disulfide nano/micron belt with the required size, orientation and thickness can be obtained by adjusting the concentration of sodium hydroxide in the mixed solution and the growth time of chemical vapor deposition. The method is simple, convenient and controllable, has low cost, and the obtained molybdenum disulfide nano/micron belt has good crystal quality and high length-width ratio, so the method has great potential in practical application.
The invention adopts molybdate solution as molybdenum source, sodium hydroxide solution as catalyst, sulfur powder as sulfur source, and is obtained by a tube furnace chemical vapor deposition method; by adjusting different proportions of the sodium molybdate and the sodium hydroxide mixed solution, the controllable adjustment of the size and the orientation of the nanometer/micrometer band can be realized; the adjustment of the number of nano/micron band layers can be realized by adjusting the growth time; finally, the high aspect ratio molybdenum disulfide nanometer/micrometer bands with different sizes, orientations and layers are controllably obtained on the substrate.
The invention discloses a controllable preparation method of a high-aspect-ratio molybdenum disulfide nano/micron belt, which comprises the following steps:
(1) Preparing a mixed solution of sodium molybdate and sodium hydroxide in a specific proportion
Preparing sodium molybdate and sodium hydroxide mixed solutions with different proportions according to the requirements of different sizes and orientations of the required growing molybdenum disulfide nano/micron bands; wherein, the concentration of sodium molybdate is constant at 7.5mM (mmol/L), and the concentration of sodium hydroxide is regulated according to the growth requirement, and the specific steps are as follows: (1) sodium hydroxide concentration 1mM: nanoribbons oriented symmetrically along six-fold, with widths below 1 μm; (2) sodium hydroxide concentration 1.5mM: a micrometer band oriented in double symmetry, the width of which is 2-10 mu m; (3) sodium hydroxide concentration 5mM: the width of the netlike disordered micro-strip is 2-10 mu m;
namely: when the concentration of sodium hydroxide in the mixed solution is 1mM, six-fold symmetrical orientation growth of the nanobelt is obtained;
when the concentration of sodium hydroxide in the mixed solution is more than 1mM and less than 1.5mM, six-fold symmetrically oriented grown nanobelts and double-fold symmetrically oriented grown micrometer belts are obtained;
when the concentration of sodium hydroxide in the mixed solution was 1.5mM, a micrometer band oriented in double symmetry was obtained;
when the concentration of sodium hydroxide in the mixed solution is more than 1.5mM and less than 5mM, a micrometer band oriented in double symmetry and a network micrometer band grown in disorder are obtained;
when the concentration of sodium hydroxide in the mixed solution is 5mM or more and 7mM or less, a network-like micro-strip grown in disorder is obtained.
(2) Substrate pretreatment and source solution spin coating
Sequentially ultrasonically cleaning the cut sapphire substrate in acetone, isopropanol and deionized water for 15min, and blow-drying with nitrogen; then treating for 5min by an oxygen plasma processor; dripping the prepared mixed solution on a substrate, spin-coating for 90 seconds at a rotating speed of 2000rpm, and naturally air-drying;
(3) Chemical vapor deposition method of growth
Placing the spin-coated substrate with the front face facing downwards in a quartz boat, placing the substrate in a third temperature zone in a 3-inch three-temperature zone tube furnace; simultaneously placing a ceramic boat containing 400mg of sulfur powder in a first temperature zone at the upstream side, wherein the distance between the ceramic boat and the ceramic boat is 50cm; after vacuumizing and gas washing, controlling the gas flow of carrier gas (nitrogen) to be 250sccm, maintaining the gas pressure at normal pressure, and heating the three temperature areas from room temperature to 200 ℃, 350 ℃ and 850 ℃ respectively; and maintaining a certain growth time according to the number of layers of the molybdenum disulfide nano/micron belt to be obtained, wherein a single-layer molybdenum disulfide nano/micron belt is mainly obtained after maintaining for 5min, and a multi-layer molybdenum disulfide nano/micron belt is mainly obtained after maintaining for 10min and above.
In some embodiments, the concentration of sodium molybdate in the mixed solution is constant, and the change of the size and orientation of the molybdenum disulfide nano/micro band can be realized by adjusting the change of the concentration of sodium hydroxide in the mixed solution, which is as follows: six-fold symmetrical oriented growth nanoribbons, to doubly symmetrical oriented growth nanoribbons, to disordered growth network nanoribbons.
In some embodiments, the variation in the number of layers of molybdenum disulfide nano/micro ribbons can be achieved by adjusting the growth time during chemical vapor deposition: the single-layer molybdenum disulfide nanobelt or micrometer belt growing for 5min and below, the single-layer molybdenum disulfide nanobelt or micrometer belt containing single layer and multiple layers simultaneously is obtained in the period of 5-10 min, and the multiple-layer molybdenum disulfide nanobelt/micrometer belt mainly grows in the period of 10min and above.
In some embodiments, in the spin coating process, the set rotation speed is 1000 rpm-3000 rpm, and the spin coating time is more than 60 s.
In some embodiments, in the chemical vapor deposition process, the reaction temperature in the first temperature region is set to be 150 ℃ to 250 ℃, the reaction temperature in the second temperature region is set to be 300 ℃ to 400 ℃, and the reaction temperature in the third temperature region is set to be 700 ℃ to 850 ℃.
The molybdenum disulfide nano/micron band obtained by the invention grows on the surface of a substrate (preferably sapphire), wherein the width of the nano band is 200 nm-1000 nm, and the length is 20-60 mu m; the width of the micrometer band is 2-10 mu m, and the length can reach 700 mu m at the longest. The aspect ratio of the nanometer/micrometer band can reach more than 100.
The following are specific examples
Example 1
As shown in fig. 1 and 2, the molybdenum disulfide nano/micro belt has a very high aspect ratio and good crystal quality. As shown in FIG. 1, the scanning electron microscopic image shows that the narrowest part of the nano/micron band of molybdenum disulfide is only 200nm, and the length can reach more than 50 μm, which indicates that the aspect ratio can exceed 100 and exceeds most of the nano/micron bands of molybdenum disulfide obtained by the current technical proposal. The X-ray photoelectron spectroscopy shown in fig. 2 confirms that the obtained molybdenum disulfide material is indeed molybdenum disulfide material, and the number ratio of molybdenum atoms to sulfur atoms is 1:1.95, the molybdenum disulfide nano/micron band has fewer sulfur vacancies, and the better crystal quality is proved.
In this example, a mixed solution of sodium molybdate having a concentration of 7.5mM (mmol/L) and sodium hydroxide having a concentration of 1mM was spin-coated on the cleaned and oxygen plasma-treated sapphire substrate at a rotation speed of 2000rpm for 90 seconds; then the mixture is placed in a chemical vapor deposition system, the reaction temperatures of the three temperature areas are respectively set to 200 ℃, 350 ℃ and 850 ℃, and the growth time is 5min.
Example 2
With reference to fig. 3, the technical scheme for controllably preparing the molybdenum disulfide nano/micro belt provided by the invention mainly comprises the following steps:
(1) Step one: preparation of sodium molybdate and sodium hydroxide mixed solution
Firstly, dissolving weighed sodium molybdate powder into deionized water to obtain a constant-proportion sodium molybdate solution. Then, a certain mass of sodium hydroxide particles are continuously added into the mixture to obtain a mixed solution of sodium molybdate and sodium hydroxide with the required concentration. In these mixed solutions, the concentration of sodium molybdate was constant at 7.5mM (mmol/L), and the concentration of sodium hydroxide was between 1mM and 7mM, three concentrations of 1mM, 1.5mM and 5mM were selected to exhibit a remarkable difference effect.
(2) Step two: substrate pretreatment and source solution spin coating
The method adopts a sapphire substrate. Firstly, ultrasonic cleaning is carried out on the raw materials in acetone, isopropanol and deionized water in sequence, and then the raw materials are dried by a nitrogen gun. Then treating for 5min by an oxygen plasma processor to enhance the wettability of the substrate; and then dripping the prepared mixed solution on the substrate, spin-coating for 90 seconds at a rotating speed of 2000rpm, and naturally air-drying to obtain the substrate uniformly distributed with the molybdenum source and the catalyst.
The concentration of the dropwise added mixed solution is selected according to the growth requirement, and the specific steps are as follows: (1) sodium hydroxide concentration 1mM: nanoribbons oriented symmetrically along six-fold, with widths below 1 μm; (2) sodium hydroxide concentration 1.5mM: a micrometer band oriented in double symmetry, the width of which is 2-10 mu m; (3) sodium hydroxide concentration 5mM: the width of the netlike disordered micro-strip is 2-10 mu m.
(3) Step three: chemical vapor deposition method for growing molybdenum disulfide nano/micron belt
The method selects a three-temperature-zone chemical vapor deposition system with a three-inch pipe diameter. Firstly, placing the spin-coated substrate with the front face facing downwards in a quartz boat for placing horizontally, and placing the substrate in the center of a third temperature area; then 400mg of sulfur powder is weighed, and the sulfur powder is contained in a ceramic boat, and is placed in a first temperature zone at the upstream side, wherein the distance between the sulfur powder and a substrate is 50cm; then, the chemical vapor deposition system was turned on, and after the vacuum was applied and the gas was purged, the flow rate of the carrier gas (nitrogen) was controlled to 250sccm, and the atmospheric pressure was maintained at normal pressure. The three temperature zones were warmed up from room temperature at a rate of 30 c/min to 200 c, 350 c and 850 c, respectively, and maintained for a specific growth time. And after the reaction is finished, naturally cooling the system to room temperature, and taking out a sample to obtain the molybdenum disulfide nano/micro belt with the required size, orientation and layer number.
According to the number of layers of the molybdenum disulfide nano/micron belt which is needed to be obtained, the length of the growth time is required to be adjusted, and the method specifically comprises the following steps: (1) If a single-layer molybdenum disulfide nano/micron band is to be obtained, the growth time is set to be 5min; (2) If a multilayer molybdenum disulfide nano/micro band is to be obtained, the growth time is set to 10min and above.
Example 3
In this embodiment, the size and orientation of the molybdenum disulfide nano/micro bands are controlled and controlled for growth. As shown in FIG. 4, (a-c) in FIG. 4 is an optical microscopic image of a molybdenum disulfide nano/micro belt obtained by spin-coating with a mixed solution of sodium molybdate concentration of 7.5mM and sodium hydroxide concentration of 1mM, 1.5mM and 5mM, respectively, and growing for 5 minutes by chemical vapor deposition at a growth temperature set at 200 ℃/350 ℃/850 ℃. The specific growth steps are as described above. When the concentration of sodium hydroxide is 1mM, nanobelts grown along six-fold symmetrical orientation are mainly obtained, with a width of less than 1 μm; when the concentration of sodium hydroxide is 1.5mM, a micron band grown in a double symmetrical orientation with a width of 2 to 10 μm is mainly obtained; whereas when the sodium hydroxide concentration was 5mM, a disordered network of micro bands was obtained, with a width of 2 to 10. Mu.m.
Example 4
In the embodiment, the number of layers of the molybdenum disulfide nano/micron belt is controlled and regulated and grows. As shown in fig. 5, (a) in fig. 5 and (b) in fig. 5 are optical microscopic images of molybdenum disulfide nano/micro bands obtained by spin coating using a mixed solution of sodium molybdate concentration of 7.5mM and sodium hydroxide concentration of 1.5mM, and growing for 5min and 10min, respectively, in a chemical vapor deposition system having a growth temperature set at 200 ℃/350 ℃/850 ℃. The specific growth steps are as described above. When the growth time is controlled to be 5min, a single-layer molybdenum disulfide nano/micron band is mainly obtained; when the growth time is controlled to be 10min, a multi-layer molybdenum disulfide nano/micro band is mainly obtained.
Example 5
In this example, phototransistors were prepared based on primarily grown molybdenum disulfide nano/micro ribbons, and were tested for electrical and photoelectric properties to highlight the beneficial effects of the present invention. Spin coating is carried out by adopting a mixed solution of sodium molybdate with the concentration of 7.5mM and sodium hydroxide with the concentration of 1mM, and a molybdenum disulfide nano/micron band obtained by growing for 5min is grown in a chemical vapor deposition system with the growth temperature set at 200 ℃/350 ℃/850 ℃ and is prepared into a photoelectric transistor device by a micro-nano processing technology. As shown in fig. 6, fig. 6 (a) and fig. 6 (b) are the electrical and optoelectronic properties, respectively, of the phototransistor device, indicating that the device has a very high current to switch ratio (9×10) 5 ) Excellent responsivity (8.6A/W) and specific detection rate (9.8X10) 12 Jones)。
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A controllable preparation method of molybdenum disulfide nanobelts or micrometer belts, which is characterized by comprising the following steps:
(1) Spin-coating a mixed solution of a molybdenum source and sodium hydroxide serving as a catalyst on a substrate to obtain a substrate uniformly distributed with the molybdenum source and the catalyst, wherein the molybdenum source is sodium molybdate or ammonium molybdate;
(2) Placing the substrate obtained in the step (1) in a third temperature zone of a three-temperature-zone chemical vapor deposition device, and placing sulfur powder in a first temperature zone, wherein the third temperature zone and the first temperature zone are separated by a second temperature zone; vacuumizing the three-temperature-zone chemical vapor deposition device, and then washing gas to enable air flow to blow from the direction of the first temperature zone to the direction of the third temperature zone; and then heating to sublimate the sulfur powder in the first temperature zone into a gaseous state, generating a sodium molybdenum oxide intermediate by the spin-coating on the substrate in the third temperature zone, and reacting the gaseous sulfur with the sodium molybdenum oxide intermediate to obtain the molybdenum disulfide nanobelt or the molybdenum disulfide micrometer belt.
2. The controllable preparation method of molybdenum disulfide nanobelts or microband according to claim 1, characterized in that when the concentration of sodium hydroxide in the mixed solution is 1mM, six-fold symmetrical orientation grown nanobelts are obtained;
when the concentration of sodium hydroxide in the mixed solution is more than 1mM and less than 1.5mM, six-fold symmetrically oriented grown nanobelts and double-fold symmetrically oriented grown micrometer belts are obtained;
when the concentration of sodium hydroxide in the mixed solution was 1.5mM, a micrometer band oriented in double symmetry was obtained;
when the concentration of sodium hydroxide in the mixed solution is more than 1.5mM and less than 5mM, a micrometer band oriented in double symmetry and a network micrometer band grown in disorder are obtained;
when the concentration of sodium hydroxide in the mixed solution is 5mM or more and 7mM or less, a network-like micro-strip grown in disorder is obtained.
3. The controllable preparation method of the molybdenum disulfide nanobelt or the micron belt according to claim 1 or 2, wherein in the step (2), when the growth time is less than or equal to 5min, a single-layer molybdenum disulfide nanobelt or a single-layer molybdenum disulfide micron belt is obtained; when the growing time is more than 5min and less than 10min, the molybdenum disulfide nanobelts or micrometer belts containing single layers and multiple layers are obtained; when the growing time is more than or equal to 10min, the multi-layer molybdenum disulfide nano-belt or micro-belt is obtained.
4. The controllable preparation method of molybdenum disulfide nanobelts or nanobelts as claimed in claim 1, wherein the reaction temperature in the first temperature zone is 150 ℃ to 250 ℃, the reaction temperature in the second temperature zone is 300 ℃ to 400 ℃, and the reaction temperature in the third temperature zone is 700 ℃ to 850 ℃.
5. The controllable preparation method of molybdenum disulfide nanobelts or micro-belts according to claim 1, wherein in step (2), the substrate is placed in a third temperature zone of a three temperature zone chemical vapor deposition device face down, so that sodium-molybdenum-oxygen intermediates are more favorable to flow on the surface of the substrate during the growth process.
6. The controllable preparation method of molybdenum disulfide nanobelts or micrometer belts according to claim 1, characterized in that in step (1), the spin-coating speed is 1000 rpm-3000 rpm, and the time is more than 60 s.
7. The controllable preparation method of molybdenum disulfide nanobelts or micro-belts as claimed in claim 1, wherein the aspect ratio of the molybdenum disulfide nanobelts or molybdenum disulfide micro-belts is up to 100 or more.
8. The controllable preparation method of molybdenum disulfide nanobelts or nanobelts as claimed in claim 1, wherein the substrate is subjected to oxygen plasma treatment prior to spin coating.
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