CN116081580B - A method for preparing wafer-level tungsten disulfide or tungsten diselenide two-dimensional nanofilm - Google Patents
A method for preparing wafer-level tungsten disulfide or tungsten diselenide two-dimensional nanofilm Download PDFInfo
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- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002120 nanofilm Substances 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 20
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 20
- 239000010980 sapphire Substances 0.000 claims abstract description 20
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010937 tungsten Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 239000011888 foil Substances 0.000 claims description 19
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 25
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 19
- 239000002356 single layer Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 abstract 3
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 238000012512 characterization method Methods 0.000 description 31
- 239000010408 film Substances 0.000 description 26
- 238000001237 Raman spectrum Methods 0.000 description 9
- 238000005424 photoluminescence Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
- C01G41/00—Compounds of tungsten
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明公开一种晶圆级二硫化钨或二硒化钨二维纳米薄膜的制备方法。通过对蓝宝石晶圆进行高温退火处理，使处理后的蓝宝石更有利于生长高质量、大面积、高均匀性的二硫化钨和二硒化钨薄膜。采用化学气相沉积法，通过对气体流量调控、前驱体金属钨源的设计、限域高度的调节，可实现不同层厚(单层、双层或三层)的二硫化钨和二硒化钨纳米薄膜制备。包括：一、对氢气流量进行调控，可实现单、双层二硫化钨纳米薄膜的制备。本发明无需在生长过程中引入氯化物或氢氧化物等催化剂，使得晶圆级薄膜的生长更加的高效、方便，且无杂质元素的引入。The present invention discloses a method for preparing a wafer-level two-dimensional nanofilm of tungsten disulfide or tungsten diselenide. By subjecting sapphire wafers to high-temperature annealing treatment, the treated sapphire is more conducive to the growth of high-quality, large-area, and highly uniform tungsten disulfide and tungsten diselenide films. By adopting a chemical vapor deposition method, the preparation of tungsten disulfide and tungsten diselenide nanofilms with different layer thicknesses (single layer, double layer, or triple layer) can be achieved through the regulation of gas flow, the design of a precursor metal tungsten source, and the adjustment of the confinement height. The method includes: 1. The hydrogen flow rate is regulated to achieve the preparation of single-layer and double-layer tungsten disulfide nanofilms. The present invention does not need to introduce catalysts such as chlorides or hydroxides during the growth process, so that the growth of wafer-level films is more efficient and convenient, and no impurity elements are introduced.
Description
Technical Field
The invention relates to preparation of transition metal dihalide compounds, in particular to a preparation method of a wafer-level tungsten disulfide or tungsten diselenide two-dimensional nano film.
Background
Among the numerous two-dimensional materials, semiconductor transition metal dihalides are considered to be the most promising materials due to their excellent electrical and optoelectronic properties. Tungsten disulfide and tungsten diselenide, which are the transition metal dihalide compounds, have the characteristics of proper band gap size, high carrier mobility, strong light interaction, very large spin division and the like. The crystal structure is layered, each layer consists of three atomic planes, the single-layer structure is formed by forming covalent bonds between one W atom and 6 surrounding X (S/Se) atoms, and one X (S/Se) atom is combined with 3W atoms to form an 'X-W-X' sandwich structure, and the layers are combined together through van der Waals interactions. The monolayer tungsten disulfide and tungsten diselenide are direct band gap semiconductors, the band gap of the tungsten disulfide is 2.01eV, the band gap of the tungsten diselenide is 1.6eV, the size of the band gap can be reduced along with the increase of the layer number, and when the tungsten disulfide and the tungsten diselenide are more than two layers in thickness, the direct band gap is converted into the indirect band gap. In theory, a single layer of tungsten disulfide with a room temperature mobility of 1103cm 2V-1s-1 and a single layer of tungsten diselenide with a room temperature mobility of 705cm 2V-1s-1 are considered as channel materials with great potential for high performance field effect transistors.
However, one of the difficult challenges faced by van der waals materials for use in high-end electronics and optoelectronics applications is the growth from the micrometer scale to the wafer scale, which is necessary to expand the application of two-dimensional materials and to meet the demands of today's semiconductor processes.
Disclosure of Invention
Aiming at the technical problem that the nano-scale and macro-scale of the transition metal dihalide compound are not uniform enough when the transition metal dihalide compound is applied to high-end light-emitting devices, memristors and the like, the invention provides a preparation method of a wafer-level tungsten disulfide and tungsten diselenide two-dimensional nano film. The preparation of the tungsten disulfide and tungsten diselenide two-dimensional nano film with high quality wafer level and controllable layer thickness is successfully realized based on strategies such as precursor design, substrate engineering and the like by a chemical vapor deposition method. The method is simple to operate, high in repeatability and low in cost, and the process can be easily expanded to other transition metal dihalogenated compounds, so that the wafer-scale thin film further provides possibility of application in large-scale integrated devices and semiconductor industry.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The preparation method of the wafer-level tungsten disulfide and tungsten diselenide two-dimensional nano film comprises the following steps:
(1) Placing the polished sapphire on the C surface in the center of a heating zone of a tube furnace, and annealing at a high temperature of 800-1200 ℃ in an argon-oxygen mixed gas environment to obtain a sapphire substrate;
(2) Placing a metal tungsten foil in the center of a heating zone of a tube furnace, and heating and oxidizing in air to obtain a tungsten trioxide foil;
(3) According to the sequence from the upstream to the downstream of the airflow, firstly pushing an alumina boat filled with sulfur powder or selenium powder to the center of a first heating zone, and then covering a sapphire substrate with tungsten trioxide foil and pushing the tungsten trioxide foil to the center of a second heating zone;
(4) Opening an air flow valve, introducing hydrogen-argon mixed gas into the tubular furnace, and flushing the reaction cavity for 30-60 minutes before heating;
(5) Setting a programmed temperature, heating a first heating temperature region to 200-250 ℃ under the condition of hydrogen-argon mixed gas, heating a second heating temperature region to 750-800 ℃ to perform growth preparation of the wafer-level tungsten disulfide nano film, or heating the first heating temperature region to 350-400 ℃ under the condition of hydrogen-argon mixed gas, heating the second heating temperature region to 780-820 ℃ to perform growth preparation of the wafer-level tungsten diselenide nano film;
(6) And after the growth is finished, naturally cooling the tubular furnace to room temperature, and closing the hydrogen and the argon to obtain the wafer-level tungsten disulfide or tungsten diselenide nano film.
Preferably, in the step (1), the annealing time is 2-5 hours, the flow rate of oxygen in the argon-oxygen mixed gas is 80-150sccm, and the flow rate of argon is 80-150sccm.
Preferably, in step (2), the tungsten foil is oxidized in air at a temperature of 650-750 ℃ for a time of 40-70 minutes.
Preferably, in the step (3), the confinement space between the tungsten trioxide foil and the sapphire substrate is 0.2-2mm.
Preferably, in the step (4), the flow rate of the hydrogen-argon mixed gas is 120-180sccm, and the flow rate of the hydrogen is 15-30sccm.
Preferably, the growth time of the wafer-level tungsten disulfide nano film or the wafer-level tungsten diselenide nano film is 8-16 minutes.
Compared with the prior art, the invention has the following remarkable advantages:
1) Unlike the tungsten disulfide and tungsten diselenide nanometer sheet growing on silicon, glass, mica and other substrates, the invention adopts high temperature annealed C-plane sapphire as the substrate, and can realize the growth preparation of the wafer-level size tungsten disulfide and tungsten diselenide two-dimensional nanometer film by regulating and controlling the annealing time and annealing conditions.
2) Different from hydrothermal method, liquid phase stripping and other methods, the method adopts a chemical vapor deposition method, and can accurately prepare tungsten disulfide and tungsten diselenide two-dimensional nano films with different layer thicknesses through regulating and controlling the growth temperature, hydrogen flow and confined space.
3) The tungsten source precursor is designed, and unlike the conventional method of using the trioxide powder as the tungsten source, the method of the invention uses the tungsten foil oxidized in the air as the tungsten source, and the tungsten source is flat and smooth, and is a face-to-face growth mode of the metal source and the substrate, so that the uniformity of diffusion of the tungsten source is improved in the growth process, and the method is more beneficial to preparing the high-uniformity and high-quality film.
4) Compared with other wafer-level growth methods, the method does not add catalysts such as hydroxide or chloride, avoids the introduction of impurity elements, and realizes the preparation of the wafer-level two-dimensional nano film with high quality and high uniformity.
Drawings
FIG. 1 is a digital image of a two-dimensional nano film of wafer-level tungsten disulfide prepared by a chemical vapor deposition method corresponding to example 1;
FIG. 2 is a graph showing the optical characterization result of a two-dimensional nano-film of wafer-level tungsten disulfide prepared by the chemical vapor deposition method corresponding to example 1;
FIG. 3 is a Raman characterization result of a wafer-level tungsten disulfide two-dimensional nano-film prepared by a chemical vapor deposition method corresponding to example 1;
FIG. 4 is a Kelvin probe microscope characterization result of a wafer-level tungsten disulfide two-dimensional nano-film prepared by the chemical vapor deposition method corresponding to example 1;
FIG. 5 is a graph showing the results of the X-ray photoelectron spectroscopy of a two-dimensional nano-film of wafer-level tungsten disulfide prepared by the chemical vapor deposition method corresponding to example 1;
FIG. 6 shows the results of Raman spectrum characterization of different layers of wafer-level tungsten disulfide two-dimensional nano-films prepared by the chemical vapor deposition method corresponding to example 2;
FIG. 7 shows photoluminescence characterization results of different layers of a wafer-level tungsten disulfide two-dimensional nano film prepared by a chemical vapor deposition method corresponding to example 2;
FIG. 8 is the atomic force microscope characterization results of different numbers of layers of wafer-level tungsten disulfide two-dimensional nano-films prepared by the chemical vapor deposition method corresponding to example 2;
FIG. 9 is a digital photograph of a two-dimensional nano-film of wafer-level tungsten diselenide prepared by the chemical vapor deposition method corresponding to example 3;
FIG. 10 is a graph showing the optical characterization result of a two-dimensional nano-film of wafer-level tungsten diselenide prepared by the chemical vapor deposition method corresponding to example 3;
FIG. 11 is a Raman characterization result of a wafer-level tungsten diselenide two-dimensional nano-film prepared by a chemical vapor deposition method corresponding to example 3;
FIG. 12 is a Kelvin probe microscope characterization result of a two-dimensional nano-film of wafer-level tungsten diselenide prepared by the chemical vapor deposition method corresponding to example 3;
FIG. 13 is a graph showing the results of the X-ray photoelectron spectroscopy of the two-dimensional nano-film of wafer-level tungsten diselenide prepared by the chemical vapor deposition method corresponding to example 3;
FIG. 14 shows the results of Raman spectrum characterization of different layers of the wafer-level tungsten diselenide two-dimensional nano-film prepared by the chemical vapor deposition method corresponding to example 4;
FIG. 15 is a graph showing the photoluminescence characterization results of different numbers of layers of a wafer-level tungsten diselenide two-dimensional nano-film prepared by the chemical vapor deposition method corresponding to example 4;
fig. 16 is an atomic force microscope characterization result of different layers of the wafer-level tungsten diselenide two-dimensional nano-film prepared by the chemical vapor deposition method corresponding to example 4.
Detailed Description
The invention will now be described in further detail with reference to the drawings and specific examples, to which the invention is not limited.
Example 1
And (3) placing the C-plane sapphire wafer into a tube furnace for high-temperature annealing at 1000 ℃ for 3 hours, wherein the atmosphere in the tube furnace is oxygen-argon mixed gas, the oxygen flow is 100sccm, and the argon flow is 100sccm. And taking out the sapphire wafer as a growth substrate after naturally cooling to room temperature. Then, the tungsten foil was put into a tube furnace and heated in an air atmosphere at a temperature of 700 ℃ for a duration of 40 minutes, to obtain an oxidized tungsten foil as a metal tungsten source. 250mg of sulfur powder was placed in an alumina boat as a sulfur source. And then covering the oxidized tungsten foil on the annealed sapphire wafer face to face, wherein the space limit height of the oxidized tungsten foil and the annealed sapphire wafer is 1mm, pushing the sapphire wafer into the center of the second heating temperature zone, and pushing an alumina boat containing sulfur powder into the center of the first heating temperature zone. Then, 250sccm argon gas was introduced into the tube furnace for 45 minutes to stabilize the gas atmosphere in the reaction chamber, and then a hydrogen-argon mixed gas was introduced, wherein the flow rate of the hydrogen gas was 20sccm and the flow rate of the argon gas was 150sccm. Setting a programmed temperature to enable the center of the first heating temperature zone to reach 250 ℃, enabling the center of the second heating temperature zone to reach 800 ℃ and enabling the growth time to be 12 minutes. And after the growth is finished, naturally cooling to room temperature, and closing the hydrogen and the argon, and taking out the sapphire substrate.
The resulting wafer level tungsten disulfide film is grown as shown in fig. 1. And (3) carrying out optical microscope, raman spectrum, atomic force microscope and Kelvin probe microscope characterization on the tungsten disulfide film, wherein the results are shown in figures 2-5. As can be seen from the optical microscope characterization result graph, the scratch is a sapphire substrate, the uniformity of the grown film is high, and the surface is smooth and flat. The Raman spectrum characterization result shows that the two characteristic peaks E 2g and A 1g are respectively 354cm -1、419cm-1, the characteristic peaks are consistent with the reported data, and the grown film is a tungsten disulfide film. As shown by the atomic force microscope and Kelvin probe microscope characterization results, the surface of the film is flat and smooth, the roughness is small, and the surface potential distribution is uniform. From the X-ray photoelectron spectra, the W4 f and S2 p orbit fitted curves tested were respectively matched to their standard binding energy fitted curves.
Example 2
The growth procedure of example 1 was maintained, and the preparation of a single layer tungsten disulfide film was achieved by reducing the hydrogen flow to 15sccm, with other experimental conditions unchanged. FIG. 6 is a Raman spectrum characterization, wherein the peak frequency difference of two characteristic peaks of the single-layer tungsten disulfide is 62cm -1, which is consistent with the reported data of the single-layer tungsten disulfide. The single layer of tungsten diselenide shows a direct band gap and a strong response to photoluminescence, and fig. 7 shows photoluminescence characterization, and the tungsten diselenide shows a strong luminous efficiency. The atomic force microscope characterization result of fig. 8 shows that the thickness of the tungsten disulfide film is 0.82nm, and the characterization result can prove that the single-layer tungsten disulfide film is successfully prepared. The growth process and experimental conditions of example 1 are maintained, and the preparation of the double-layer tungsten disulfide film can be realized. The double-layer tungsten disulfide presents an indirect band gap, has weak photoluminescence response, and the peak frequency difference between two characteristic peaks of a Raman spectrum of the double-layer tungsten disulfide is 64cm -1. Figures 6, 7 demonstrate this for both photoluminescence and raman spectral characterization. FIG. 8 atomic force microscope characterization, the bilayer tungsten disulfide film thickness was 1.7nm. The growth procedure and experimental conditions of example 1 were maintained, and the preparation of a three-layer tungsten disulfide film was achieved by changing the tungsten foil oxidation conditions to 700 ℃ for 60 minutes. The growth process and experimental conditions of example 1 were continued to be maintained, and the preparation of a bulk tungsten disulfide film was achieved by reducing the height of the confinement space to 0.2 mm. The tri-layer and bulk tungsten disulfide also exhibit indirect band gaps, are substantially nonresponsive to photoluminescence, and the raman spectral characteristic peaks of tungsten disulfide will exhibit an E 2g red shift, an a 1g blue shift. These features are demonstrated in both fig. 6 and 7. FIG. 8 is an atomic force microscope characterization of three-layer and bulk tungsten disulfide thin films with thicknesses of 2.2nm and 7.2nm.
Example 3
The high temperature annealing of the sapphire wafer, oxidation of the metal tungsten foil and experimental procedure were identical to example 1. 200mg of selenium powder is put into an alumina boat as a selenium source, the space limit height of a tungsten foil and a sapphire wafer is 1mm, hydrogen-argon mixed gas is introduced, the hydrogen flow is 12sccm, and the argon flow is 100sccm. Setting the temperature programming to enable the center of the first heating temperature zone to reach 400 ℃, enabling the center of the second heating temperature zone to reach 800 ℃ and enabling the growth time to be 14 minutes.
The resulting wafer level tungsten diselenide film is grown as shown in fig. 9. And (3) carrying out optical microscope, raman spectrum, atomic force microscope and Kelvin probe microscope characterization on the tungsten diselenide film, wherein the results are shown in figures 10-13. As can be seen from the optical microscope characterization result graph, the grown tungsten diselenide film has high uniformity, smooth and flat surface and no impurity. From the Raman spectrum characterization, the characteristic peak E 2g/A1g is divided into 254cm -1, and the characteristic peak is consistent with the data reported in the literature, so that the grown film is proved to be a tungsten diselenide film. The atomic force microscope and the Kelvin probe microscope show that the film has uniform and smooth surface, small roughness and uniform surface potential distribution. The X-ray photoelectron spectrum shows that the W4 f and Se 3d orbit fitting curves respectively accord with the standard binding energy fitting curves.
Example 4
The growth procedure of example 3 was maintained, and the preparation of a single-layer tungsten diselenide film was achieved by reducing the growth temperature to 780 ℃ with other experimental conditions unchanged. Fig. 14 is a raman spectrum characterization, with a peak frequency of 252cm -1 for the characteristic peak of single layer tungsten diselenide, consistent with the single layer tungsten diselenide report data. The single layer of tungsten diselenide exhibits a direct band gap and a strong response to photoluminescence, and fig. 15 shows photoluminescence characterization, and the tungsten diselenide exhibits a strong luminous efficiency. The atomic force microscope characterization result of fig. 16 shows that the thickness of the tungsten diselenide film is 0.87nm, and the characterization result can prove that the single-layer tungsten diselenide film is successfully prepared. The growth process and experimental conditions of example 3 are maintained, so that the preparation of the double-layer tungsten diselenide film can be realized. The growth process and experimental conditions of example 3 were continued to be maintained, and the preparation of three-layer, multi-layer tungsten diselenide films was achieved by reducing the height of the confinement space to 0.6mm and 0.2 mm. Bilayer, trilayer and bulk tungsten diselenide exhibit indirect band gaps, are weak in photoluminescent response, and the raman spectral characteristic peak of tungsten diselenide exhibits E 2g/A1g blue shift. These features are also demonstrated in both fig. 14 and 15. FIG. 8 is an atomic force microscope characterization of double, triple and bulk tungsten disulfide thin films with thicknesses of 1.54mm, 2.4nm and 3.3nm.
Claims (5)
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