One-dimensional coaxial heterostructure composite material, preparation method and application thereof

Abstract

This invention discloses a one-dimensional coaxial heterostructure composite material, its preparation method, and its applications. The one-dimensional coaxial heterostructure composite material comprises: a nanotube with a cavity structure, and a one-dimensional embedded material uniformly embedded within the cavity structure of the nanotube. The one-dimensional embedded material includes one or more combinations of molybdenum sulfide, molybdenum selenide, and molybdenum telluride, forming a coaxial heterostructure between the nanotube and the embedded material. The preparation method of this invention efficiently synthesizes the one-dimensional coaxial heterostructure composite material on a substrate using chemical vapor deposition. This method is simple, versatile, and has the potential for large-area preparation. The prepared one-dimensional coaxial heterostructure composite material has advantages such as high quality and good uniformity, ensuring the convenience of synthesizing the one-dimensional heterostructure and providing a new material foundation for the development and application of embedded one-dimensional materials in nanoelectronics, nanooptics, and other fields.

Description

Technical Field

[0001] This invention belongs to the field of low-dimensional materials and nano-optoelectronic semiconductor materials technology, specifically relating to a composite material with a one-dimensional coaxial heterostructure, its preparation method and application. Background Technology

[0002] Molybdenum sulfide, with its two-dimensional layered structure and excellent photoelectric, catalytic, and mechanical properties, shows great promise for applications in nanoelectronic devices, optoelectronic devices, and flexible sensing. In particular, recent years have seen breakthroughs in the research of two-dimensional molybdenum sulfide optoelectronic devices (Nature 2025, 640, 654), combined with advancements in the synthesis and characterization techniques of low-dimensional nanomaterials (Nat. Nanotechnol. 2023, 18, 529), significantly promoting fundamental research and application exploration in the field of one-dimensional optoelectronic materials. However, the synthesis of one-dimensional molybdenum sulfide currently faces challenges such as synthesis difficulties and low growth efficiency.

[0003] Boron nitride nanotubes, due to their unique hollow tubular structure and excellent chemical stability, thermal stability, and insulation properties, are considered ideal templates for the synthesis of one-dimensional nanomaterials. Existing techniques for preparing molybdenum sulfide / boron nitride heterojunctions mainly focus on the stacking of mechanically exfoliated boron nitride and molybdenum sulfide. However, due to further reductions in dimensionality, this method is difficult to implement in the construction of one-dimensional molybdenum sulfide and its heterojunctions. Although there are studies on the epitaxial growth of molybdenum sulfide on the outside of boron nitride nanotubes (Science 2020, 367, 537), this method is difficult to synthesize and has low efficiency. Furthermore, existing nanotube-filling synthesis techniques are not applicable to compound systems such as metal sulfides, and the size of the filling material is insufficient to meet the current research and application needs in the optoelectronic field. To date, researchers have synthesized various one-dimensional nanomaterials using the internal cavity structure of boron nitride nanotubes (CN101789300A, Science 2018, 361, 263). Currently, the synthesis methods for one-dimensional materials based on boron nitride nanotubes still suffer from problems such as complex processes, difficult preparation, low yield, and poor performance. Furthermore, there is a lack of methods for the inlay synthesis of one-dimensional molybdenum sulfide, and existing technologies cannot effectively meet the development needs of one-dimensional molybdenum sulfide. Therefore, new and efficient methods for the preparation of one-dimensional molybdenum sulfide urgently need to be developed. Summary of the Invention

[0004] The main objective of this invention is to provide a one-dimensional coaxial heterostructure composite material and its preparation method, thereby overcoming the shortcomings of the prior art.

[0005] Another object of the present invention is to provide the application of the one-dimensional coaxial heterostructure composite material.

[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes: A first aspect of the present invention provides a one-dimensional coaxial heterostructure composite material, comprising: a nanotube having a cavity structure, and a one-dimensional embedded material uniformly embedded within the cavity structure of the nanotube, wherein the one-dimensional embedded material comprises one or more combinations of molybdenum sulfide, molybdenum selenide and molybdenum telluride, and the nanotube and the embedded material form a coaxial heterostructure.

[0007] A second aspect of the present invention provides a method for preparing the one-dimensional coaxial heterostructure composite material, comprising: placing any one of a sulfur source, a selenium source, and a tellurium source, along with a molybdenum source and a nanotube, sequentially along the direction of the working gas in the reaction chamber of a chemical vapor deposition apparatus, heating to carry out a deposition reaction, and obtaining a one-dimensional coaxial heterostructure composite material.

[0008] A third aspect of the present invention provides the application of the one-dimensional coaxial heterostructure composite material in the fields of nanoelectronics, nanooptics, photodetectors or optoelectronic devices.

[0009] Compared with the prior art, the present invention has at least the following beneficial effects: 1) The preparation method of the present invention uses nanotubes as growth templates and precise temperature and atmosphere control by vapor deposition method to prepare high-quality one-dimensional coaxial heterostructure composite materials. 2) Compared with existing techniques that epitaxially grow molybdenum sulfide on the surface of boron nitride nanotubes, this invention successfully achieves one-dimensional molybdenum sulfide synthesis inside boron nitride nanotubes with dimensions fully compatible with current electronic device fabrication processes and low-dimensional material optics research methods, significantly reducing the difficulty of one-dimensional optoelectronic material research from a materials perspective. Furthermore, the one-dimensional coaxial heterostructure composite material prepared by this invention is of high quality and can be used in research and applications such as photodetectors and high-performance electronic devices. These material advantages provide a new material foundation for the development of multiple fields such as low-dimensional material nanoelectronics, nanooptics, and optoelectronic devices. 3) The synthesis process provided by this invention has the advantages of simple process, mild reaction conditions and good repeatability while ensuring structural controllability and functionality. It overcomes the problems of complex process and high vacuum requirements of traditional preparation methods, and is more suitable for laboratory research and development and potential pilot-scale production. It provides technical guidance for the commercial production of low-dimensional heterojunction materials. 4) The preparation method provided by this invention has compatibility with a variety of materials and is applicable to the preparation of various embedded heterojunctions, providing a broader material basis for the development of low-dimensional material optoelectronics. Attached Figure Description

[0010] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0011] Figure 1 This is a schematic diagram illustrating the synthesis of the one-dimensional molybdenum sulfide embedded boron nitride nanotube heterostructure MoS2@BNNT in Example 1 of the present invention. Figure 2 This is a SEM image of the one-dimensional molybdenum sulfide-embedded boron nitride nanotube heterostructure prepared in Example 1 of the present invention; Figure 3 The image shows the AFM morphology of the one-dimensional molybdenum sulfide-embedded boron nitride nanotube heterostructure prepared in Example 1 of this invention. Figure 4 EDX elemental images of the one-dimensional molybdenum sulfide-embedded boron nitride nanotube heterostructure prepared in Example 1 of this invention; Figure 5 The image shows the Raman spectral characterization results of the one-dimensional molybdenum sulfide embedded boron nitride nanotube heterostructure prepared in Example 1 of this invention. Detailed Implementation

[0012] In view of the problems of low synthesis efficiency and poor quality of existing one-dimensional molybdenum sulfide heterojunction materials, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The main point is to provide a simple and efficient synthesis method compatible with current low-dimensional electronic material and device fabrication processes, which efficiently synthesizes one-dimensional coaxial heterostructure composite materials on a substrate via chemical vapor deposition. This method is simple, has good universality, and has the potential for large-area fabrication. The prepared heterostructure composite materials have advantages such as high quality and good uniformity. This method not only ensures the convenience of synthesizing one-dimensional heterostructures but also provides a new material foundation for the development and application of embedded one-dimensional materials in nanoelectronics, nanooptics, and other fields.

[0013] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0014] Specifically, as one aspect of the technical solution of the present invention, the one-dimensional coaxial heterostructure composite material involved includes: a nanotube with a cavity structure, and a one-dimensional embedded material uniformly embedded in the cavity structure of the nanotube, wherein the one-dimensional embedded material includes one or more combinations of molybdenum sulfide, molybdenum selenide and molybdenum telluride, and a coaxial heterostructure is formed between the nanotube and the embedded material.

[0015] In some embodiments, the nanotubes may include one or more combinations of carbon nanotubes (CNTs), boron nitride nanotubes (BNNTs), etc.

[0016] In some implementations, the diameter of the heterostructure is approximately 5 to 30 nm, and its length is on the micrometer scale.

[0017] As another aspect of the technical solution of the present invention, it also relates to a method for preparing the one-dimensional coaxial heterostructure composite material, which includes: placing any one of a sulfur source, a selenium source, and a tellurium source, along with a molybdenum source and a nanotube, in the reaction chamber of a chemical vapor deposition device in sequence along the direction of the working gas, heating up to carry out a deposition reaction, and obtaining a one-dimensional coaxial heterostructure composite material.

[0018] In some implementations, the preparation method includes: setting any one of the sulfur source, selenium source, tellurium source, etc., in a first region, setting a molybdenum source in a second region, setting a nanotube in a third region, and introducing a working gas into the reaction chamber, wherein the first region, the second region, and the third region are arranged sequentially along the direction of travel of the working gas.

[0019] In some embodiments, the preparation method includes: heating the temperature of the first region, the second region, and the third region gradually. Specifically, the temperature of the first region is 200~500℃, the temperature of the second region is 500~600℃, and the temperature of the third region is 700~900℃. The first region is used to achieve the volatilization of the sulfur source (the temperatures corresponding to the selenium source and tellurium source increase sequentially), controlling the supply of the sulfur source; the second temperature region is a suitable temperature for the volatilization of the molybdenum source, controlling the supply of the molybdenum source; and the third temperature region is used for the growth of the one-dimensional coaxial heterostructure composite material.

[0020] In some embodiments, the sulfur source includes, but is not limited to, sulfur (S) powder.

[0021] In some implementations, the selenium source includes selenium (Se) powder, but is not limited to this.

[0022] In some implementations, the tellurium source includes tellurium (Te) powder, but is not limited to this.

[0023] In some embodiments, the molybdenum source includes MoO3, but is not limited to this.

[0024] Furthermore, the nanotubes are defined as described above.

[0025] In some implementations, the deposition reaction takes 0.5 to 2 hours.

[0026] Furthermore, the preparation method includes: purging the air in the reaction chamber with an inert gas before heating.

[0027] Furthermore, the working gas includes a mixture of inert gas and hydrogen.

[0028] In some more specific embodiments, the preparation method of the one-dimensional coaxial heterostructure composite material includes the following steps: (1) In a tubular furnace, a quartz boat loaded with sulfur powder and BNNT is placed upstream and in the center of the temperature zone; (2) Another quartz ship carries an appropriate amount of MoO3 powder (99.9% purity) and places it between the two; (3) First, purge the furnace system with inert gas; (4) Heat the sulfur powder region and the substrate region to 200 ℃ and 900 ℃ respectively; (5) Introduce a mixture of inert gas and H2 and maintain the reaction for 2 hours; (6) After the reaction is complete, the product is naturally cooled to room temperature and a one-dimensional coaxial heterostructure composite material (MoS2@BNNT) can be collected on the substrate.

[0029] Furthermore, the substrate materials used in this invention include, but are not limited to, silicon wafers, quartz, sapphire, etc. Besides being applicable to boron nitride nanotubes, it is also suitable for filling other nanotubes on the substrate surface, such as carbon nanotubes. In addition to molybdenum sulfide, by replacing the corresponding selenium and tellurium sources, the embedded materials are also applicable to the synthesis of one-dimensional molybdenum selenide and one-dimensional molybdenum telluride materials.

[0030] In summary, the preparation method of the present invention uses nitrogen nanotubes as templates and is carried out by chemical vapor deposition. The process is simple, highly controllable, easy to streamline and scale up, and has universality, making it suitable for the preparation of various one-dimensional coaxial heterostructures.

[0031] The one-dimensional coaxial heterostructure composite material prepared by this invention has large size and good quality, providing a material for the study of the optoelectronic properties of one-dimensional molybdenum sulfide.

[0032] As another aspect of the technical solution of this invention, it also relates to the application of the one-dimensional coaxial heterostructure composite material. Specifically, the one-dimensional coaxial heterostructure composite material prepared by this invention has high quality and can be used in research and applications such as photodetectors and high-performance electronic devices. These material advantages provide a new material foundation for the development of low-dimensional materials in nanoelectronics, nanooptics, optoelectronic devices, and other diverse fields.

[0033] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0034] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0035] Example 1 The experimental setup in this embodiment is in accordance with... Figure 1 The preparation method of a one-dimensional molybdenum sulfide embedded boron nitride nanotube heterostructure includes the following steps: (1) In a tubular furnace, a quartz vessel loaded with sulfur (S) powder (purity >99.99%) and BNNT is placed upstream and in the center of the temperature zone; (2) Another quartz ship carried 0.1 g of MoO3 powder (99.9% purity) and placed it between the two; (3) First, purge the furnace system with 300 sccm of Ar gas for 3 minutes; (4) Heat the sulfur powder region and the substrate region to 200 ℃ and 900 ℃ respectively, and heat the MoO3 powder region to 500 ℃; (5) Introduce a mixture of Ar and H2 gas and maintain the reaction for 2 hours; (6) After the reaction is complete, the product is naturally cooled to room temperature and a one-dimensional molybdenum sulfide embedded boron nitride nanotube heterostructure (labeled as MoS2@BNNT) can be collected on the substrate.

[0036] In this embodiment, the product MoS2@BNNT showed a clear bright line in the middle of the nanotube under SEM (scanning electron microscopy), indicating that one-dimensional molybdenum sulfide was successfully synthesized within the nanotube. Figure 2 As shown.

[0037] Figure 3 The image shows the AFM morphology of the product MoS2@BNNT. AFM (atomic force microscopy) revealed that the outer surface of the nanotubes was clean and free of any deposits.

[0038] The inventors in this case used STEM EDX (Energy Loss Spectroscopy) to image elements and clearly observed that sulfur and molybdenum were uniformly encapsulated by boron and nitrogen, verifying the structure of molybdenum sulfide embedded in boron nitride nanotubes. Figure 4 As shown.

[0039] In addition, the inventors in this case verified the embedded structure using Raman spectroscopy, and the Raman spectroscopy characterization results are as follows: Figure 5 As shown, the spectrum displays both the Raman peaks of the boron nitride tube (e.g.) Figure 5 (a) also shows the Raman peaks of molybdenum sulfide (as shown in the figure). Figure 5 (b) shown).

[0040] Example 2 The preparation method of the one-dimensional molybdenum sulfide embedded carbon nanotube heterostructure in this embodiment includes the following steps: (1) In a tubular furnace, a quartz ship loaded with sulfur (S) powder (purity >99.99%) and CNTs is placed upstream and in the center of the temperature zone; (2) Another quartz ship carried 0.1 g of MoO3 powder (99.9% purity) and placed it between the two; (3) First, purge the furnace system with 300 sccm of Ar gas for 3 minutes; (4) Heat the sulfur powder region and the substrate region to 200 ℃ and 700 ℃ respectively, and heat the MoO3 powder region to 500 ℃; (5) Introduce a mixture of Ar and H2 gas and maintain the reaction for 2 hours; (6) After the reaction is complete, the product is naturally cooled to room temperature and a one-dimensional molybdenum sulfide embedded boron nitride nanotube heterostructure (labeled as MoS2@CNT) can be collected on the substrate.

[0041] Example 3 The preparation method of the one-dimensional molybdenum selenide embedded boron nitride nanotube heterostructure in this embodiment includes the following steps: (1) In a tube furnace, a quartz boat loaded with selenium (Se) powder (purity >99.99%) and BNNT is placed upstream and in the center of the temperature zone; (2) Another quartz ship carried 0.1 g of MoO3 powder (99.9% purity) and placed it between the two; (3) First, purge the furnace system with 300 sccm of Ar gas for 3 minutes; (4) Heat the selenium powder region and the substrate region to 350 °C and 900 °C respectively, and heat the MoO3 powder region to 600 °C; (5) Introduce a mixture of Ar and H2 gas and maintain the reaction for 0.5 hours; (6) After the reaction is complete, the product is naturally cooled to room temperature and a one-dimensional molybdenum selenide embedded boron nitride nanotube heterostructure (labeled as MoSe@BNNT) can be collected on the substrate.

[0042] Example 4 The preparation method of the one-dimensional molybdenum telluride embedded boron nitride nanotube heterostructure in this embodiment includes the following steps: (1) In a tube furnace, a quartz boat loaded with tellurium (Te) powder (purity >99.99%) and BNNT is placed upstream and in the center of the temperature zone; (2) Another quartz ship carried 0.1 g of MoO3 powder (99.9% purity) and placed it between the two; (3) First, purge the furnace system with 300 sccm of Ar gas for 3 minutes; (4) The tellurium powder region and the substrate region are heated to 500 °C and 900 °C respectively, and the MoO3 powder region is heated to 600 °C; (5) Introduce a mixture of Ar and H2 gas and maintain the reaction for 2 hours; (6) After the reaction is complete, the product is naturally cooled to room temperature and a one-dimensional molybdenum telluride embedded boron nitride nanotube heterostructure (labeled as MoTe@BNNT) can be collected on the substrate.

[0043] Tests showed that the SEM images, AFM morphology diagrams, and Raman spectroscopy characterization results of the products obtained in Examples 2-4 were similar to those in Example 1, proving the formation of an embedded structure. This invention successfully synthesized a nanotube-embedded one-dimensional coaxial heterostructure composite material.

[0044] In addition, the inventors of this case also conducted experiments with other raw materials and conditions listed in this specification, referring to the aforementioned embodiments, and similarly obtained a one-dimensional coaxial heterostructure composite material with advantages such as high quality and good uniformity.

[0045] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A one-dimensional coaxial heterostructure composite material, characterized in that, include: A nanotube with a cavity structure and a one-dimensional embedded material uniformly embedded within the cavity structure of the nanotube, wherein the one-dimensional embedded material includes one or more combinations of molybdenum sulfide, molybdenum selenide and molybdenum telluride, and the nanotube and the embedded material form a coaxial heterostructure.

2. The one-dimensional coaxial heterostructure composite material according to claim 1, characterized in that: The nanotubes include one or more combinations of carbon nanotubes and boron nitride nanotubes.

3. The method for preparing a one-dimensional coaxial heterostructure composite material as described in any one of claims 1 to 2, characterized in that, include: One of the sulfur source, selenium source, and tellurium source, along with a molybdenum source and nanotubes, is sequentially placed in the reaction chamber of a chemical vapor deposition apparatus along the direction of the working gas. The mixture is heated to carry out a deposition reaction, thereby obtaining a one-dimensional coaxial heterostructure composite material.

4. The preparation method according to claim 3, characterized in that: Any one of the sulfur source, selenium source, and tellurium source is disposed in the first region, the molybdenum source is disposed in the second region, and the nanotube is disposed in the third region. Working gas is introduced into the reaction chamber, and the first region, the second region, and the third region are arranged sequentially along the direction of travel of the working gas.

5. The preparation method according to claim 4, characterized in that: The temperature is gradually increased in the first, second, and third regions. Preferably, the temperature of the first region is 200-500℃, the temperature of the second region is 500-600℃, and the temperature of the third region is 700-900℃.

6. The preparation method according to claim 3 or 4, characterized in that: The sulfur source includes sulfur powder; and / or, the selenium source includes selenium powder; and / or, the tellurium source includes tellurium powder. And / or, the molybdenum source includes MoO3.

7. The preparation method according to claim 3 or 4, characterized in that: The nanotubes include one or more combinations of carbon nanotubes and boron nitride nanotubes.

8. The preparation method according to claim 4, characterized in that: The working gas includes a mixture of inert gas and hydrogen.

9. The preparation method according to claim 3, characterized in that: The deposition reaction takes 0.5 to 2 hours.

10. The application of the one-dimensional coaxial heterostructure composite material according to any one of claims 1 to 2 in the fields of nanoelectronics, nanooptics, photodetectors or optoelectronic devices.

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