CN114293172A - Preparation method of molybdenum disulfide pattern - Google Patents
Preparation method of molybdenum disulfide pattern Download PDFInfo
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- CN114293172A CN114293172A CN202210024954.0A CN202210024954A CN114293172A CN 114293172 A CN114293172 A CN 114293172A CN 202210024954 A CN202210024954 A CN 202210024954A CN 114293172 A CN114293172 A CN 114293172A
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Abstract
The invention provides a preparation method of a molybdenum disulfide pattern, which comprises the following steps: cutting a Mo foil graph with a proper size; oxidizing the Mo foil graph by using an electrochemical anodic oxidation method; MoS growth by modified chemical vapor deposition2And (6) a graph. The method is used for preparing MoS2The patterns have the advantages of simple operation, high practicability, various patterns and flexible positions, and can be used for preparing MoS with large area and uniform thin layer2Film pattern, etc.
Description
Technical Field
The invention belongs to the field of preparation of two-dimensional thin-layer materials, and particularly relates to a preparation method of a molybdenum disulfide pattern with a large-area thin layer and uniformity.
Background
MoS2The semiconductor material is a low-dimensional wide-band gap semiconductor material, the band gap has thickness dependence, and the semiconductor material shows great advantages in electronic device application due to the characteristics of excellent semiconductor performance (high on-off ratio and mobility), proper band gap width, high stability and the like, and meanwhile, the planar structure of the semiconductor material enables the semiconductor material to be expected to be applied to electronic devices. However, there are also limitations in application, such as high quality, large area MoS2The film preparation is relatively unstable and the cost is higher; in addition, the practical device is realized by various circuit patterns, and the prefabricated matched material patterns are required to be designed according to the requirements of different device structures, so that the MoS2The exploration of the pattern growth method is a necessary requirement for realizing the construction of the device, and the pattern growth is a premise of array growth, so that a foundation can be laid for improving the performance research from a single device stage to an integrated device stage. Therefore, the method is mainly used for preparing the large-area high-quality thin-layer uniform MoS with a specific pattern by pretreating the Mo foil pattern by an electrochemical anodic oxidation method and an improved chemical vapor deposition method through a confined space method2A film.
Disclosure of Invention
The invention aims to overcome the defects of the prior art method and realize MoS by a novel method2And (6) synthesizing the graph. Firstly, pre-treating Mo foil with a specific pattern, and then preparing the MoS with a large area and a uniform thin layer by adopting an improved chemical vapor deposition method2And (5) a pattern film. The preparation process is simple and easy to implement, and the obtained MoS2The pattern film is of good quality, thin and uniform.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a molybdenum disulfide pattern comprises the following steps:
(1) customizing a Mo foil with a specific pattern;
(2) pretreatment of the Mo foil: oxidizing Mo foil into MoO by electrochemical anode oxidation methodxA precursor;
(3) placing the Mo foil pretreated in the step (2) on a specified substrate by using a modified Mo foilChemical vapor deposition method for MoS growth2And (6) a graph.
The method comprises the following specific steps:
(1) cutting a customized Mo foil with a specific pattern into a shape with a proper size, and carrying out ultrasonic treatment on the Mo foil in absolute ethyl alcohol and water for 2-3 times, wherein each time lasts for 10-30 min, so as to remove impurities such as organic pollutants on the surface of the Mo foil;
(2) pretreatment of the Mo foil: and oxidizing the cleaned Mo foil by an electrochemical anodic oxidation method, wherein the whole oxidation process is carried out in a three-electrode oxidation system, the Mo foil is a working electrode, a platinum sheet is a counter electrode, a calomel electrode is a reference electrode, and the Mo foil is placed in a special electrolyte for oxidation, the electroplating voltage is about 0.4-0.7V, and the electroplating time is about 5-25 min. After the electroplating is finished, taking the oxidized Mo foil out of the electrolyte, soaking and cleaning the Mo foil in deionized water, and naturally drying the Mo foil; the electrolyte composition was 0.15 mol/L H2C2O4•2H2O、0.1 mol/L Na2SO4And 0.01 mol/L NaF, weighing the mass corresponding to each component according to the volume of the electrolyte solvent (deionized water) each time, dissolving the components in the solvent under the action of ultrasonic stirring to obtain clear electrolyte, and placing the clear electrolyte in a long-neck flask for storage and later use.
(3) With SiO2/Si or Al2O3And (3) taking sublimed sulfur and the Mo foil oxidized in the step (2) as a growth source, weighing 0.5-2 g of sublimed sulfur, loading the sublimed sulfur in a corundum boat, placing the corundum boat in an upstream area, heating by using an external heating belt, placing the oxidized Mo foil on the substrate in a flat laying mode, placing a substrate with the same size as the growth substrate above the Mo foil, and then placing the substrate on the quartz boat together and placing the substrate in a single-temperature-zone tubular furnace central temperature zone to finish the chemical vapor deposition growth process. The whole process is carried out under the argon atmosphere, the flow rate of argon is 50-100 sccm, argon is firstly introduced for 15 min to exhaust the air in the tube, then the tube furnace is heated to 750-plus-temperature 1000 ℃ at the heating rate of 10-40 ℃/min, the temperature is kept for 10-50 min, when the tube furnace is heated to 600-plus-temperature 800 ℃, the sulfur powder heating zone (130-plus-temperature 170 ℃) is started, after the tube furnace is naturally cooled to a certain temperature (200-plus-temperature 350 ℃), the furnace door is opened, the heating zone is closed, and the sample is taken out after the temperature is reduced to the room temperature.
The invention has the following remarkable advantages:
the invention is based on an electrochemical anodic oxidation method and an improved chemical vapor deposition method, wherein the electrochemical anodic oxidation method is used for pretreating Mo foil to obtain MoOxAnd (3) precursor. Because the oxidation reaction of the Mo foil is carried out from the surface to the inside and the oxidation degrees of the Mo foils at different depths are different, the obtained MoOxThe precursor is rich in multi-valence oxides with different melting points and is distributed layer by layer, and the two precursors can jointly ensure MoOxGradually and properly supplied, reacts with the simple substance S at proper temperature, and is beneficial to high-quality MoS2Layer-by-layer growth of (1). In addition, MoO can be modulated by varying plating conditionsxThe valence and the oxidation depth of the Mo source are controlled, so that the supply time and the effective amount of the Mo source are controlled, and the control of MoS is facilitated2The growth of (2).
Chemical vapor deposition method for MoS growth2In the process of patterning, a substrate is covered on the preprocessed Mo foil to form a limited area, so that the molybdenum source can be effectively prevented from losing, and the MoS with a complete pattern can be obtained2The method has the characteristics of novelty and simplicity, and can obtain MoS with large area, thin single layer and uniformity2The pattern film is helpful for promoting the application research of electronic devices.
The invention relates to the direct use of MoO3MoS is grown by taking powder and S powder as raw materials through a chemical vapor deposition method2Compared with the method, the method can obtain the MoS with the specific pattern2Thin film, directly in MoO3Preparation of MoS by using powder as raw material2Film, presence of MoS2The film grows at will, and the appearance and the size of the film are uncontrollable, namely the prepared MoS cannot be controlled2Pattern and size of film not suitable for use with specific MoS requirements2And constructing an electronic device with a thin film pattern.
Drawings
In FIG. 1, (a) and (c) are Al2O3MoS of different patterns grown on a substrate2(ii) a film physical map, (b) and (d) are corresponding optical micrographs at 10 x;
FIG. 2 (a) is an optical microscopic image of Mo foil after pretreatment at 100 timesLike (b) is Al2O3Corresponding MoS grown on a substrate2Optical microscope images at 100 times of the pattern;
FIG. 3 is a synthetic MoS2A Raman spectrum of the patterned film;
FIG. 4 (a) shows the large-area MoS grown2An optical microscope image of the film under 400 times, and (b) is a Raman mapping image corresponding to the image (a);
FIG. 5 is a synthetic MoS2AFM images of the patterned films.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Cutting a customized Mo foil with a specific pattern into a shape with a proper size, and carrying out ultrasonic treatment for 2 times in absolute ethyl alcohol and water for about 10 min each time to remove impurities such as organic pollutants on the surface of the Mo foil;
(2) pretreatment of the Mo foil: and oxidizing the cleaned Mo foil by adopting an electrochemical anodic oxidation method, wherein the whole oxidation process is carried out in a three-electrode oxidation system, the Mo foil is a working electrode, a platinum sheet is a counter electrode, a calomel electrode is a reference electrode, and the Mo foil is placed in a special electrolyte for oxidation, the electroplating voltage is about 0.52V, and the electroplating time is about 15 min. After the electroplating is finished, taking the oxidized Mo foil out of the electrolyte, soaking and cleaning the Mo foil in deionized water, and naturally drying the Mo foil; wherein the electrolyte has a composition of 0.15 mol/L H2C2O4•2H2O、0.1 mol/L Na2SO4And 0.01 mol/L NaF;
(3) with Al2O3Taking sublimed sulfur and the Mo foil oxidized in the step (2) as a growth source as a growth substrate, weighing 1.0 g of sublimed sulfur, loading the sublimed sulfur in a corundum boat, placing the corundum boat in an upstream area, heating the corundum boat by using an external heating belt, placing the oxidized Mo foil on the substrate in a flat-laying mode, and placing Al with the same size as the growth substrate above the Mo foil2O3And the substrates are then placed on a quartz boat together and placed in a central temperature area of a single-temperature-area tubular furnace to finish the chemical vapor deposition growth process. Whole courseThe method comprises the steps of conducting the process under the argon atmosphere, wherein the argon flow rate is 100 sccm, introducing argon for 15 min to exhaust air in a tube, heating the tube furnace to 860 ℃ at the temperature rising rate of 30 ℃/min, keeping the temperature for 25 min, starting a sulfur powder heating belt (160 ℃) when the tube furnace is heated to 700 ℃, turning off the heating belt when the tube furnace is naturally cooled to 280 ℃, simultaneously opening a furnace door to rapidly cool, and taking out a sample after cooling.
In FIG. 1, (a) and (c) are Al2O3Mo foil and MoS with two different patterns grown on substrate2Film material object picture, middle dark area on the substrate is grown MoS2The shape of the thin film is consistent with that of the right Mo foil, and the size of the thin film is about 8.1 mm multiplied by 3.5 mm; (b) and (d) optical micrographs at 10 times the local area of the sample in (a) and (c), respectively, most of the area showing a different whitish color from the substrate, and MoS2The color of the area where the film is positioned is consistent, which indicates that the uniform MoS with large area and single layer is successfully grown2And (5) a pattern film. In FIG. 2, (a) shows an optical microscope image at 100 times of the pretreated Mo foil, and (b) shows Al2O3Corresponding MoS grown on a substrate2Optical microscope images at 100 times of the pattern; comparison of the two figures shows the MoS2The growth shape was roughly consistent with the shape of the Mo foil, and the film was uniform. FIG. 3 is a composite MoS with a specific pattern2The Raman spectrum of the film shows that the peak position of the characteristic peak is 382 cm-1And 403 cm-1Consistent with the literature, it can therefore be determined that MoS is obtained2Film, peak separation between the next two characteristic peaks 19 cm-1It was also confirmed to be a single layer MoS2. FIG. 4 (a) shows the large-area MoS grown2Optical microscope image of film at 400 x, white area to the right as grown MoS2The left gray region is Al2O3The substrate is a uniform off-white single-layer MoS in most areas2(ii) a (b) Is a Raman mapping chart corresponding to the chart (a), and a white area on the right is a grown MoS2Left dark gray area as base, MoS2The film showed a uniform off-white color at the location, indicating that the MoS was prepared2The uniformity is improved, and the uniformity is improved,the quality is high. FIG. 5 is a synthetic MoS2The AFM image of the film is shot in the range of 5 mu m multiplied by 5 mu m, and in (a), the surface of the film is relatively clean, the thickness is 0.89 nm through software measurement, and the MoS prepared by the experiment is shown within the error2The film is a uniform monolayer.
Example 2
(1) Cutting a customized Mo foil with a specific pattern into a rectangle with the size of 15 multiplied by 20 mm, and carrying out ultrasonic treatment for 3 times in absolute ethyl alcohol and water for about 10 min each time so as to remove impurities such as organic pollutants on the surface of the Mo foil;
(2) pretreatment of the Mo foil: the clean Mo foil is oxidized by adopting an electrochemical anodic oxidation method, the whole oxidation process is carried out in a three-electrode oxidation system, the Mo foil is a working electrode, a platinum sheet is a counter electrode, a calomel electrode is a reference electrode, the three-electrode oxidation system is placed in a special electrolyte for oxidation, the electroplating voltage is about 0.58V, and the electroplating time is about 10 min. After the electroplating is finished, taking the oxidized Mo foil out of the electrolyte, soaking and cleaning the Mo foil in deionized water, and naturally drying the Mo foil; wherein the electrolyte has a composition of 0.15 mol/L H2C2O4•2H2O、0.1 mol/L Na2SO4And 0.01 mol/L NaF;
(3) with SiO2Taking the/Si as a growth substrate, taking sublimed sulfur and the Mo foil oxidized in the step (2) as a growth source, weighing 1.5 g of sublimed sulfur to be loaded in a corundum boat and placed in an upstream area, heating by using an external heating belt, placing the oxidized Mo foil on the substrate in a flat laying mode, and placing a SiO foil with the same size as the growth substrate above the Mo foil2And the/Si substrates are placed on a quartz boat together and placed in a central temperature area of the single-temperature-area tubular furnace to finish the chemical vapor deposition growth process. The whole process is carried out in an argon atmosphere, the argon flow rate is 100 sccm, argon is firstly introduced for 15 min to exhaust air in the tube, then the tube furnace is heated to 820 ℃ at the heating rate of 40 ℃/min and is kept for 35 min, when the tube furnace is heated to 660 ℃, a sulfur powder heating belt (160 ℃) is started, after the tube furnace is naturally cooled to 280 ℃, the heating belt is closed, the furnace door is opened to rapidly cool, and a sample is taken out after cooling.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. A preparation method of a molybdenum disulfide pattern is characterized by comprising the following steps: the method comprises the following steps:
(1) customizing a Mo foil with a specific pattern;
(2) pretreatment of the Mo foil: oxidizing Mo foil into MoO by electrochemical anode oxidation methodxA precursor;
(3) placing the Mo foil pretreated in the step (2) on a specified substrate, and growing MoS with a specific pattern by adopting an improved chemical vapor deposition method2。
2. The method of claim 1, wherein: the method comprises the following specific steps:
(1) cutting a customized Mo foil with a specific pattern into a shape with a proper size, and carrying out ultrasonic treatment on the Mo foil in absolute ethyl alcohol and water for 2-3 times, wherein each time lasts for 10-30 min, so as to remove impurities on the surface of the Mo foil;
(2) pretreatment of the Mo foil: oxidizing the cleaned Mo foil by adopting an electrochemical anodic oxidation method, wherein the whole oxidation process is carried out in a three-electrode oxidation system, the Mo foil is a working electrode, a platinum sheet is a counter electrode, a calomel electrode is a reference electrode, the Mo foil is placed in a special electrolyte for oxidation, the electroplating voltage is 0.4-0.7V, the electroplating time is 5-25 min, and after the electroplating is finished, the oxidized Mo foil is taken out of the electrolyte, soaked in deionized water, cleaned and naturally dried;
(3) with SiO2/Si or Al2O3Taking sublimed sulfur and the Mo foil pretreated in the step (2) as a growth source as a growth substrate, carrying the sublimed sulfur in a corundum boat, placing the corundum boat in an upstream area, heating by using an external heating belt, placing the pretreated Mo foil on the substrate in a flat spreading mode, placing a substrate with the same size as the growth substrate above the Mo foil, then placing the substrate on a quartz boat together, placing the substrate in a single-temperature-zone tubular furnace central temperature zone, finishing the chemical vapor deposition growth process, wherein the whole process is carried out in an argon atmosphere, and argon is used as an argon atmosphereIntroducing argon gas at a flow rate of 50-100 sccm for 15 min to exhaust the air in the tube, heating the tube furnace to 750-.
3. The method of claim 2, wherein: the composition of the electrolyte was 0.15 mol/L H2C2O4•2H2O、0.1 mol/L Na2SO4And 0.01 mol/L NaF.
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Cited By (3)
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| CN114807897A (en) * | 2022-04-25 | 2022-07-29 | 湘潭大学 | 1T' MoTe 2 Preparation method of nano film |
| CN115020118A (en) * | 2022-07-20 | 2022-09-06 | 兰州大学 | Preparation method of composite electrode material, super capacitor and battery |
| CN115161616A (en) * | 2022-05-26 | 2022-10-11 | 湘潭大学 | Large-area double-layer 3R phase MX 2 Preparation method of nanosheet |
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