TRANSITION METAL CHALCOGENIDE THIN-LAYER MATERIAL, PREPARATION METHOD AND APPLICATION THEREOF

Abstract

Disclosed are a transition metal chalcogenide thin-layer material, a preparation method and an application thereof. The preparation method comprises: uniformly spreading a transition metal source between two substrates to prepare a sandwich structure; performing a heat treatment on the sandwich structure to fuse and bond the two substrates together, and performing a chemical vapor deposition reaction on a chalcogen element source and the fused and bonded sandwich structure under the protection of a protective gas, wherein the transition metal source is heated to dissolve and diffuse at a reaction temperature, separated out from surfaces of the substrates, and reacts with the chalcogen element source. The prepared thin-layer material is uniformly distributed in a centimeter-level substrate.

Claims

1. A preparation method for a transition metal chalcogenide thin-layer material, comprising: S1: uniformly spreading a transition metal source between two substrates to prepare a sandwich structure; S2: performing a heat treatment on the sandwich structure to fuse and bond the two substrates together; and S3: performing a chemical vapor deposition reaction on a chalcogen element source and the sandwich structure treated in S2 under the protection of a protective gas; wherein the transition metal source is heated to dissolve and diffuse at a reaction temperature, separated out from surfaces of the substrates, and reacts with the chalcogen element source; and the chalcogen element source comprises one or more of a sulfur source, a selenium source and a tellurium source.

2. The preparation method for the transition metal chalcogenide thin-layer material according to claim 1, wherein the transition metal source includes at least one of a molybdenum source, a tungsten source, a vanadium source, a rhenium source, a tantalum source, a niobium source, a titanium source, a platinum source and a palladium source.

3. The preparation method for the transition metal chalcogenide thin-layer material according to claim 1, wherein the sulfur source includes at least one of a solid-phase sulfur source, a liquid-phase sulfur source and a gas-phase sulfur source.

4. The preparation method for the transition metal chalcogenide thin-layer material according to claim 1, wherein a mass ratio of the transition metal source to the chalcogen element source is 1:(10 to 300).

5. The preparation method for the transition metal chalcogenide thin-layer material according to claim 1, wherein the substrate is a glass substrate; and preferably, a material of the glass substrate includes at least one of soda-lime glass, potassium glass, aluminum-magnesium glass, lead-potassium glass, borosilicate glass and quartz glass.

6. The preparation method for the transition metal chalcogenide thin-layer material according to claim 5, wherein the two substrates comprise a bottom substrate and an upper substrate, a thickness of the bottom substrate ranges from 0.01 mm to 50.00 mm, and a thickness of the upper substrate ranges from 0.01 mm to 0.50 mm; and preferably, areas of the two substrates are both 1 cm.sup.2 to 100 cm.sup.2, and a load amount of the transition metal source on the substrates is 0.2 mg/cm.sup.2 to 10 mg/cm.sup.2.

7. The preparation method for the transition metal chalcogenide thin-layer material according to claim 1, wherein in S2, a temperature of the heat treatment is 100° C. to 720° C.

8. The preparation method for the transition metal chalcogenide thin-layer material according to claim 1, wherein in S3, the chemical vapor deposition reaction is performed at 0.05 Torr to 1,000 Torr, 200° C. to 780° C., and under the protection of a protective gas; and the protective gas is one or more of nitrogen, helium, neon, argon, krypton, xenon, radon, hydrogen and carbon dioxide.

9. A transition metal chalcogenide thin-layer material, wherein the transition metal chalcogenide thin-layer material is prepared by the preparation method for the transition metal chalcogenide thin-layer material according to claim 1.

10. A device comprising the transition metal chalcogenide thin-layer material according to claim 9, wherein the device is an electronic device, an optical device, an optoelectronic device, a chemical and biological sensor or an electrochemical catalytic device.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly explain the technical solutions in the examples of the present disclosure, the drawings in the description of the examples will be briefly explained below.

[0033] FIG. 1 is a schematic diagram of a preparation method for a large-area uniform molybdenum disulfide thin-layer material in Example 1 of the present disclosure;

[0034] FIG. 2 is a schematic principle diagram of the preparation method for the large-area uniform molybdenum disulfide thin-layer material in Example 1 of the present disclosure; FIG. 2(a) shows that two glass substrates are fused and bonded together by heat treatment; FIG. 2(b) shows that the molybdenum source is heated and dissolved, and then diffused to the periphery and the surfaces of the substrates driven by a thermal field, and then separated out on the surfaces of the substrates; FIG. 2(c) shows that a chemical vapor deposition reaction is performed between the sulfur source and the molybdenum source separated out on the surfaces of the substrates for nucleation under the protection of the protective gas; FIG. 2(d) shows that after nucleation, the molybdenum source is further grown to obtain the large-area uniformly-distributed molybdenum disulfide thin-layer material;

[0035] FIG. 3 is an optical micrograph of the large-area uniform molybdenum disulfide thin-layer material prepared in Example 1 of the present disclosure;

[0036] FIG. 4 is a scanning electron micrograph of the large-area uniform molybdenum disulfide thin-layer material prepared in Example 1 of the present disclosure;

[0037] FIG. 5 is a laser Raman spectrum of the large-area uniform molybdenum disulfide thin-layer material prepared in Example 1 of the present disclosure;

[0038] FIG. 6 is an X-ray photoelectron spectrum of the large-area uniform molybdenum disulfide thin-layer material prepared in Example 1 of the present disclosure;

[0039] FIG. 7 is a uniform distribution diagram of the large-area uniform molybdenum disulfide thin-layer material prepared in Example 1 of the present disclosure on a 10 mm×10 mm glass substrate;

[0040] FIG. 8 is a photoluminescence diagram of the large-area uniform molybdenum disulfide thin-layer material prepared in Example 1 of the present disclosure;

[0041] FIG. 9 is an optical micrograph and a laser Raman spectrum of a tungsten disulfide thin-layer material prepared in Example 3, wherein FIG. 9(a) shows the optical micrograph and FIG. 9(b) shows the laser Raman spectrum;

[0042] FIG. 10 is an optical micrograph and a laser Raman spectrum of a molybdenum diselenium thin-layer material prepared in Example 4, wherein FIG. 10(a) shows the optical micrograph and FIG. 10(b) shows the laser Raman spectrum;

[0043] FIG. 11 is an optical micrograph and a laser Raman spectrum of a molybdenum tungsten disulfide (Mo.sub.xW.sub.1-xS.sub.2) alloy prepared in Example 6, wherein FIG. 11(a) shows the optical micrograph and FIG. 11(b) shows the laser Raman spectrum;

[0044] FIG. 12 is a photoluminescence diagram of a molybdenum disulfide thin-layer material prepared in Comparative example 1; and

[0045] FIG. 13 is an optical micrograph of different positions P1 to P4 on the molybdenum disulfide thin-layer material prepared in Comparative example 1.

DETAILED DESCRIPTION

[0046] The present disclosure will be further explained with reference to the specific examples below. It should be understood that these examples are only used to illustrate the present disclosure and are not used to limit the scope of the present disclosure. Moreover, after reading the contents taught in the present disclosure, those skilled in the art can make various changes or modifications to the present disclosure, and these equivalent forms also fall within the scope of the present disclosure as defined in the claims.

Example 1

[0047] This Example provided a large-area highly-uniform molybdenum disulfide thin-layer material and a preparation method therefor. A schematic diagram of the preparation method was as shown in FIG. 1, and the preparation method specifically included the following steps of:

[0048] (1) uniformly spreading 0.94 mg of sodium molybdate (molybdenum source) on a surface of a soda-lime glass substrate with length, width and thickness of 25 mm×10 mm×2 mm, and completely drying the soda-lime glass substrate in a blast drying oven, and then covering a soda-lime glass substrate with the same size and a thickness of 0.15 mm; and performing heat treatment in a muffle furnace at 700° C. for 30 minutes at a heating rate of 20° C./min; after the heat treatment, the two glass substrates being fused and bonded together;

[0049] (2) using the glass substrates bonded in step (1) as the substrate and the molybdenum source at the same time, placing the glass substrates in a second heating zone of a tube furnace, and placing sulfur powder (sulfur source) in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the sulfur powder being 200 mg; and

[0050] (3) introducing argon into the tube furnace in step (2) at a rate of 50 mL/min, and making a pressure in the tube furnace be 1.2 Torr by a mechanical pump; keeping a heating temperature of the first heating zone at 220° C., and heating the second heating zone to 750° C. at a heating rate of 50° C./min, wherein the sodium molybdate in the bonded glass substrates was heated to dissolve and diffuse at the reaction temperature, and was separated out on the surfaces of the glass substrates, reacted with the sulfur source volatilized from the first heating zone and entered the second heating zone for 10 minutes at the reaction temperature, and then cooled naturally under the protection of 50 mL/min argon after the reaction to obtain a large-area highly-uniform molybdenum disulfide thin-layer material on the surfaces of the substrates.

[0051] A schematic principle diagram of the preparation method above was shown in FIG. 2. Firstly, as shown in FIG. 2(a), two glass substrates were fused and bonded together by heat treatment; As shown in FIG. 2(b), the molybdenum source was heated and dissolved, and then diffused to the periphery and the surfaces of the substrates driven by a thermal field, and then separated out on the surfaces of the substrates; As shown in FIG. 2(c), a chemical vapor deposition reaction was performed between the sulfur source and the molybdenum source separated out on the surfaces of the substrates for nucleation under the protection of the protective gas; As shown in FIG. 2(d), after nucleation, the molybdenum source was further grown to obtain the large-area uniformly-distributed molybdenum disulfide thin-layer material.

[0052] The large-area uniform molybdenum disulfide thin-layer material prepared above was tested by optical microscope (OM), scanning electron microscope (SEM), Raman spectrometer (Raman) and X-ray photoelectron spectroscopy (XPS), and the results were respectively shown in FIG. 3, FIG. 4, FIG. 5 and FIG. 6 and an uniform distribution diagram and a photoluminescence diagram of the large-area uniform molybdenum disulfide thin-layer material on a 10 mm×10 mm glass substrate were shown in FIG. 7 and FIG. 8 respectively. From the results shown in FIGS. 3 to 8, it can be seen that in this Example, by adopting the “dissolving-separating out” chemical vapor deposition method, the large-area uniformly-distributed transition metal chalcogenide thin-layer material can be prepared, a distribution size of the obtained material was 20 μm to 200 μm and a thickness of the obtained material was only 0.7 nm to 20 nm.

Example 2

[0053] This Example provided a large-area highly-uniform molybdenum disulfide thin-layer material and a preparation method therefor. A schematic diagram of the preparation method included the following steps of:

[0054] (1) uniformly spreading 1.88 mg of sodium molybdate on a surface of a potassium glass substrate with length, width and thickness of 5 mm×10 mm×3 mm, and completely drying the potassium glass substrate in a blast drying oven, and then covering a soda-lime glass substrate with the same size and a thickness of 0.15 mm; and performing heat treatment in a muffle furnace at 720° C. for 30 minutes at a heating rate of 30° C./min; after the heat treatment, the two glass substrates being fused and bonded together;

[0055] (2) using the glass substrates bonded in step (1) as the substrate and the molybdenum source at the same time, placing the glass substrates in a second heating zone of a tube furnace, and placing sulfur powder (sulfur source) in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the sulfur powder being 300 mg;

[0056] (3) introducing argon into the tube furnace in step (2) at a rate of 80 mL/min, and making a pressure in the tube furnace be 1.7 Torr by a mechanical pump; keeping a heating temperature first heating zone at 180° C., and heating the second heating zone to 730° C. at a heating rate 50° C./min, wherein the sodium molybdate in the bonded glass substrates was heated to dissolve and diffuse at the reaction temperature, and was separated out on the surfaces of the glass substrates, reacted with the sulfur source volatilized from the first heating zone and entered the second heating zone for 30 minutes at the reaction temperature, and then cooled naturally after the reaction to obtain a large-area uniformly-distributed molybdenum disulfide thin-layer material on the surfaces of the substrates.

[0057] By using the same method as in Example 1, a distribution size of the molybdenum disulfide thin-layer material prepared in this Example was 20 μm to 200 μm, a thickness of the molybdenum disulfide thin-layer material was 1.4 nm to 2.8 nm, and the molybdenum disulfide thin-layer material was uniformly distributed on a surface of a 5 mm×10 mm large-area glass substrate.

Example 3

[0058] This Example provided a large-area highly-uniform tungsten disulfide thin-layer material and a preparation method therefor. A schematic diagram of the preparation method included the following steps of:

[0059] (1) uniformly spreading 0.94 mg of sodium wolframate (tungsten source) on a surface of a soda-lime glass substrate with length, width and thickness of 25 mm×10 mm×2 mm, and completely drying the soda-lime glass substrate in a blast drying oven, and then covering a soda-lime glass substrate with the same size and a thickness of 0.15 mm; and performing heat treatment in a muffle furnace at 680° C. for 30 minutes at a heating rate of 25° C./min; after the heat treatment, the two glass substrates being fused and bonded together;

[0060] (2) using the glass substrates bonded in step (1) as the substrate and the tungsten source at the same time, placing the glass substrates in a second heating zone of a tube furnace, and placing sulfur powder (sulfur source) in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the sulfur powder being 150 mg; and

[0061] (3) introducing a protective gas into the tube furnace in step (2) at a rate of 80 mL/min, introducing hydrogen into the tube furnace at a rate of 4 mL/min, and making a pressure in the tube furnace be 5 Torr by a mechanical pump; keeping a heating temperature first heating zone at 190° C., and heating the second heating zone to 750° C. at a heating rate 50° C./min, wherein the sodium wolframate in the bonded glass substrates was heated to dissolve and diffuse at the reaction temperature, and was separated out on the surfaces of the glass substrates, reacted with the sulfur source volatilized from the first heating zone and entered the second heating zone for 15 minutes at the reaction temperature, and then cooled naturally after the reaction to obtain a large-area uniformly-distributed tungsten disulfide thin-layer material on the surfaces of the substrates.

[0062] By using the same method as in Example 1, an optical micrograph and a laser Raman spectrum of the tungsten disulfide thin-layer material prepared in this Example were shown in FIG. 9, wherein FIG. 9(a) was the optical micrograph and FIG. 9(b) was the laser Raman spectrum; a distribution size of the tungsten disulfide thin-layer material was 20 μm to 200 μm, a thickness of the tungsten disulfide thin-layer material was 0.8 nm, and the tungsten disulfide thin-layer material was uniformly distributed on a surface of a 25 mm×10 mm large-area glass substrate.

Example 4

[0063] This Example provided a large-area highly-uniform molybdenum diselenium thin-layer material and a preparation method therefor. A schematic diagram of the preparation method included the following steps of:

[0064] (1) uniformly spreading 2.82 mg of sodium molybdate on a surface of a soda-lime glass substrate with length, width and thickness of 15 mm×15 mm×2 mm, and completely drying the soda-lime glass substrate in a blast drying oven, and then covering a soda-lime glass substrate with the same size and a thickness of 0.15 mm; and performing heat treatment in a muffle furnace at 650° C. for 60 minutes at a heating rate of 30° C./min; after the heat treatment, the two glass substrates being fused and bonded together;

[0065] (2) using the glass substrates bonded in step (1) as the substrate and the molybdenum source at the same time, placing the glass substrates in a second heating zone of a tube furnace, and placing selenium powder (selenium source) in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the selenium powder being 200 mg; and

[0066] (3) introducing a protective gas into the tube furnace in step (2) at a rate of 80 mL/min, introducing hydrogen into the tube furnace at a rate of 8 mL/min, and making a pressure in the tube furnace be 2 Torr by a mechanical pump; keeping a heating temperature first heating zone at 280° C., and heating the second heating zone to 750° C. at a heating rate 50° C./min, wherein the sodium molybdate in the bonded glass substrates was heated to dissolve and diffuse at the reaction temperature, and was separated out on the surfaces of the glass substrates, reacted with the selenium source volatilized from the first heating zone and entered the second heating zone for 20 minutes at the reaction temperature, and then cooled naturally after the reaction to obtain a large-area uniformly-distributed molybdenum diselenium thin-layer material on the surfaces of the substrates.

[0067] By using the same method as in Example 1, an optical micrograph and a laser Raman spectrum of the molybdenum diselenium thin-layer material prepared in this Example were shown in FIG. 10, wherein FIG. 10(a) was the optical micrograph and FIG. 10(b) was the laser Raman spectrum; a distribution size of the molybdenum diselenium thin-layer material was 20 μm to 200 μm, a thickness of the molybdenum diselenium thin-layer material was 1.4 nm to 3.0 nm, and the molybdenum diselenium thin-layer material was uniformly distributed on a surface of a 15 mm×15 mm large-area glass substrate.

Example 5

[0068] This Example provided a large-area highly-uniform rhenium doped molybdenum disulfide thin-layer material and a preparation method therefor. A schematic diagram of the preparation method included the following steps of:

[0069] (1) uniformly spreading 0.94 mg of sodium molybdate and 0.10 mg of sodium rhenate on a surface of a soda-lime glass substrate with length, width and thickness of 25 mm×15 mm×3 mm, and completely drying the soda-lime glass substrate in a blast drying oven, and then covering a soda-lime glass substrate with the same size and a thickness of 0.15 mm; and performing heat treatment in a muffle furnace at 700° C. for 30 minutes at a heating rate of 20° C./min; after the heat treatment, the two glass substrates being fused and bonded together;

[0070] (2) using the glass substrates bonded in step (1) as the substrate and the transition metal source at the same time, placing the glass substrates in a second heating zone of a tube furnace, and placing sulfur powder (sulfur source) in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the sulfur powder being 200 mg; and

[0071] (3) introducing argon into the tube furnace in step (2) at a rate of 50 mL/min, and making a pressure in the tube furnace be 1.2 Torr by a mechanical pump; keeping a heating temperature of the first heating zone at 220° C., and heating the second heating zone to 750° C. at a heating rate of 50° C./min, wherein the sodium molybdate and the sodium rhenate in the bonded glass substrates were heated to dissolve and diffuse at the reaction temperature, and were separated out on the surfaces of the glass substrates, reacted with the sulfur source volatilized from the first heating zone and entered the second heating zone for 10 minutes at the reaction temperature, and then cooled naturally after the reaction to obtain a large-area highly-uniform rhenium doped molybdenum disulfide single-layer material on the surfaces of the substrates.

[0072] By the same method as in Example 1, a distribution size of the rhenium doped molybdenum disulfide single-layer material prepared in this Example was 10 μm to 100 μm, a thickness of the rhenium doped molybdenum disulfide single-layer material was 0.7 nm to 0.8 nm, and the rhenium doped molybdenum disulfide single-layer material was uniformly distributed on a surface of a 25 mm×15 mm large-area glass substrate.

Example 6

[0073] This Example provided a large-area highly-uniform molybdenum tungsten disulfide (Mo.sub.xW.sub.1-xS.sub.2) alloy thin-layer material and a preparation method therefor. A schematic diagram of the preparation method included the following steps of:

[0074] (1) uniformly spreading 0.24 mg of sodium molybdate and 3.6 mg of sodium wolframate on a surface of a soda-lime glass substrate with length, width and thickness of 25 mm×15 mm×3 mm, and completely drying the soda-lime glass substrate in a blast drying oven, and then covering a soda-lime glass substrate with the same size and a thickness of 0.15 mm; and performing heat treatment in a muffle furnace at 660° C. for 30 minutes at a heating rate of 20° C./min; after the heat treatment, the two glass substrates being fused and bonded together;

[0075] (2) using the glass substrates bonded in step (1) as the substrate and the transition metal source at the same time, placing the glass substrates in a second heating zone of a tube furnace, and placing sulfur powder (sulfur source) in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the sulfur powder being 150 mg; and

[0076] (3) introducing argon into the tube furnace in step (2) at a rate of 50 mL/min, and making a pressure in the tube furnace be 1.2 Torr by a mechanical pump; keeping a heating temperature of the first heating zone at 150° C., and heating the second heating zone to 750° C. at a heating rate of 50° C./min, wherein the sodium molybdate and the sodium wolframate in the bonded glass substrates were heated to dissolve and diffuse at the reaction temperature, and were separated out on the surfaces of the glass substrates, reacted with the sulfur source volatilized from the first heating zone and entered the second heating zone for 10 minutes at the reaction temperature, and then cooled naturally after the reaction to obtain a large-area highly-uniform molybdenum tungsten disulfide (Mo.sub.xW.sub.1-xS.sub.2) alloy single-layer material on the surfaces of the substrates.

[0077] By using the same method as in Example 1, an optical micrograph and a laser Raman spectrum of the molybdenum tungsten disulfide (Mo.sub.xW.sub.1-xS.sub.2) alloy single-layer material prepared in this Example were shown in FIG. 11, wherein FIG. 11(a) was the optical micrograph and FIG. 11(b) was the laser Raman spectrum; a distribution size of the molybdenum tungsten disulfide alloy single-layer material was 10 μm to 20 μm, a thickness of the molybdenum tungsten disulfide alloy single-layer material was 0.7 nm to 0.8 nm, and the molybdenum tungsten disulfide alloy single-layer material was uniformly distributed on a surface of a 25 mm×15 mm large-area glass substrate.

Comparative Example 1

[0078] (1) placing 10 mg of molybdenum trioxide and a Si/SiO.sub.2 substrate in a second heating zone of a tube furnace, placing the Si/SiO.sub.2 substrate face down directly above the molybdenum trioxide, and placing sulfur powder in a first heating zone upstream of the second heating zone in the tube furnace, a use amount of the sulfur powder being 600 mg; and

[0079] (2) introducing argon into the tube furnace in step (1) at a rate of 200 mL/min, keeping a heating temperature of the first heating zone at 250° C., and heating the second heating zone to 700° C. at a heating rate of 20° C./min, keeping the temperature for 10 minutes, and naturally cooling after the reaction to obtain a molybdenum disulfide thin-layer material.

[0080] A photoluminescence diagram of the molybdenum disulfide thin-layer material prepared in Comparative example and optical micrographs of different positions P1 to P4 on the molybdenum disulfide thin-layer material were respectively tested. The obtained results were shown in FIG. 12 and FIG. 13. In FIG. 13, P1 to P4 respectively indicate that points were taken at different positions on the molybdenum disulfide thin-layer material prepared in Comparative example 1 for testing. From the results shown in FIG. 13, it can be seen that the morphologies of the samples observed at different positions were inconsistent, which indicated that the molybdenum disulfide thin-layer material prepared in Comparative example 1 was unevenly distributed.

[0081] From the above, it can be seen that the transition metal chalcogenide thin-layer material can be prepared through the present disclosure by adopting the ““dissolving-separating out” chemical vapor deposition method, and meanwhile, the doping of transition metal sulfides can also be realized. The distribution size of the obtained material can be 20 μm to 200 μm, the thickness of the obtained material is only 0.7 nm to 20 nm, and the obtained material has excellent optical and electrical properties, and has wide application prospects in the fields of electronic devices, optical devices, sensors, electrochemical catalysis and the like.

[0082] Although the present disclosure has been specifically shown and described with reference to the Examples, it should be understood by those skilled in the art that various changes can be made in form and detail without departing from the spirit and scope of the present disclosure as defined in the claims, which are the protection scope of the present disclosure.