Method and device for preparing atomic layer deposition niobium disulfide film on large specific surface area substrate

Abstract

The embodiment of the present invention discloses a method and device for preparing an atomic layer deposition niobium disulfide film on a substrate with a large specific surface area, which relates to the field of atomic layer deposition technology, can reduce the temperature required for synthesis growth, and can deposit and grow high-quality niobium disulfide films on substrates with a large specific surface area, has the advantages of simple process, stability, uniform quality, etc., and is suitable for large-scale preparation and production of niobium disulfide films. The present invention comprises: a source path I, a source path II, a reaction chamber device, and a vacuum pump (7), wherein the source path I is used to transport a Nb source to the reaction chamber device; the source path II is used to transport an S source to the reaction chamber device; the reaction chamber device is composed of a pneumatic valve V3 and a pneumatic valve V4, which are linked with the pneumatic valves V11 and V22 in the source paths I and II. After the niobium source and the sulfur source are sent into the reaction chamber, the pneumatic valves V3 and V4 are closed in time, so that the niobium source and the sulfur source can fully react in the chamber.

Description

Technical Field

[0001] The invention relates to the technical field of atomic layer deposition, and in particular to a method and a device for preparing an atomic layer deposition niobium disulfide film on a substrate with a large specific surface area. Background Art

[0002] Niobium disulfide (NbS 2 ) is a highly conductive layered transition metal sulfide that has attracted widespread attention due to its excellent mechanical, electrical and biological affinity. It has shown important application value in the field of biomolecular sensing. In order to improve the detection sensitivity of biomolecules, a large specific surface area sensing electrode structure is required. However, how to uniformly and stably modify niobium disulfide on the surface of a large specific surface area sensing electrode to give full play to its performance is a technical problem.

[0003] The existing technical methods include hydrothermal synthesis and chemical vapor deposition (CVD). Among them, the hydrothermal synthesis method produces materials of poor quality and low purity, and the material has low adhesion to the substrate surface. During the sensing process, it is easy to fall off, which seriously affects the sensing accuracy. Chemical vapor deposition (CVD) is a method of depositing niobium source (NbO 2 ) and sulfur source (S powder) are heated to generate corresponding gas precursors, and then inert gas (Ar or N 2 ) transport them to the vicinity of the substrate to form the desired niobium disulfide film on the substrate. Although this method can obtain large-area, high-quality niobium disulfide, due to the high temperature of the synthetic growth, it is necessary to maintain 650℃-1000℃ throughout the synthetic growth process, which limits its application on substrates that are not resistant to high temperatures. The high-temperature preparation environment also leads to high energy consumption in the preparation process, and the cost of large-scale preparation is difficult to control.

[0004] Therefore, how to improve the process of preparing atomic layer deposition niobium disulfide films on large specific surface area substrates, especially to reduce the temperature in the process, has become a problem that needs to be studied. Summary of the invention

[0005] The embodiments of the present invention provide a method and device for preparing an atomic layer deposition niobium disulfide film on a substrate with a large specific surface area, which can reduce the temperature required for synthetic growth, thereby reducing energy consumption.

[0006] To achieve the above object, the embodiments of the present invention adopt the following technical solutions:

[0007] In a first aspect, an embodiment of the present invention provides a method for preparing an atomic layer deposition niobium disulfide film on a substrate with a large specific surface area, comprising:

[0008] Step S1, placing the substrate in a plasma cleaning machine for treatment so as to enhance its surface energy and functionalize its surface active groups; wherein, at room temperature, the substrate can be placed in the plasma cleaning machine for treatment for 20 seconds.

[0009] Step S2, placing the substrate processed in step S1 into the reaction chamber (4), operating the vacuum pump (7) to evacuate the reaction chamber (4) and the pipeline connected to the reaction chamber (4) to maintain a certain vacuum degree, and then starting the chamber heating device (5) to heat the reaction chamber (4);

[0010] Step S3, loading the niobium source into the Nb source bottle (17), and then starting the multi-heating range collaborative heating system to heat the Nb source bottle (17) and the delivery pipeline between the Nb source bottle (17) and the reaction chamber (4);

[0011] Step S4, closing the source path II and introducing a carrier gas into the source path I, and using the carrier gas to deliver the niobium source output from the Nb source bottle (17) into the reaction chamber (4), then stopping the introduction of the carrier gas and sealing the reaction chamber (4) until a first reaction time is reached, so that the niobium source and the active functional groups on the surface of the substrate undergo self-limiting chemical adsorption to form a chemical functional group layer containing niobium on the substrate; after the first preset time is reached, introducing the carrier gas into the source path I again and connecting the reaction chamber (4), so that the reaction byproducts and residual niobium source in the reaction chamber (4) are flushed by the carrier gas introduced into the reaction chamber (4) again; wherein the first reaction time ∈ [1s, 30s], that is, stopping the introduction of the carrier gas and sealing the reaction chamber (4) so ​​that the time for the niobium source to react with the substrate in the reaction chamber (4) does not exceed 30s.

[0012] Step S5, closing the source path I and introducing a carrier gas into the source path II, and using the carrier gas to deliver the sulfur source output from the S source bottle (11) into the reaction chamber (4), then stopping the introduction of the carrier gas and sealing the reaction chamber (4) until a second reaction time is reached, so that the sulfur source and the niobium layer formed in step S4 undergo a self-limiting chemical reaction, thereby generating a niobium disulfide atomic layer on the substrate, and after the second preset time is reached, introducing a carrier gas into the source path II again and connecting the reaction chamber (4), so that the reaction byproducts and residual sulfur source in the reaction chamber (4) are flushed by the carrier gas introduced into the reaction chamber (4) again; wherein the second reaction time ∈ [1s, 30s], i.e., stopping the introduction of the carrier gas and sealing the reaction chamber (4) so ​​that the time for the sulfur source to react with the substrate in the reaction chamber (4) does not exceed 30s.

[0013] Step S6, repeating steps S4 to S5 until the thickness of the niobium disulfide film deposited on the surface of the substrate reaches a preset value.

[0014] Afterwards, steps S4 and S5 can be repeated according to the required thickness of the niobium disulfide film. Steps S4 and S5 include two self-limiting chemical reactions, forming a complete niobium disulfide atomic layer deposition cycle. The number of cycles of steps S4 and S5 is controlled to control the thickness of the final deposited niobium disulfide film.

[0015] In a preferred embodiment, the material type of the substrate includes at least carbon fiber paper and nickel metal foam; the substrate has a large specific surface area, and the value of the large specific surface area is greater than or equal to 0.5m 2 / g.

[0016] Specifically, in step S1, the substrate is placed in a plasma cleaning machine for treatment, so that the surface of the substrate is functionalized, and the functionalization includes hydroxylation or thiolization.

[0017] Specifically, in step S2, the vacuum pump (7) evacuates the reaction chamber (4) so ​​that the vacuum degree of the reaction chamber (4) is maintained in a range of greater than or equal to 1 and less than or equal to 1000 Pa; the chamber heating device (5) heats the reaction chamber (4) to a temperature T5, and T5∈[200°C, 500°C]. In practical applications, as long as the vacuum degree can meet the atomic layer deposition process, it is preferably controlled within a range of 1 to 1000 Pa; the specific heating temperature of the heating reaction chamber is determined according to the specific niobium source and sulfur source, and is preferably controlled within a range of 200-500 degrees Celsius.

[0018] In a preferred embodiment, the niobium source is niobium organic metal or tantalum halide. For example, the niobium source is niobium hexacarbonyl, niobium fluoride or niobium chloride; the S source needs to have self-limiting chemical reaction ability, and can be organic matter containing mercapto groups and its plasma, such as hydrogen sulfide, dialkyl disulfide or dihalogenated disulfide.

[0019] In a preferred embodiment, the flow rate of the carrier gas is 10 mL / min to 500 mL / min; in step S4, the time for the niobium source output from the Nb source bottle (17) to be fed into the reaction chamber (4) by the carrier gas is 0.1 s to 5 s; the time for the carrier gas to be fed into the reaction chamber (4) again to flush the reaction chamber (4) is 1 s to 20 s. In step S5, the time for the sulfur source output from the S source bottle (17) to be fed into the reaction chamber (4) by the carrier gas is 0.1 s to 5 s; the time for the carrier gas to be fed into the reaction chamber (4) again to flush the reaction chamber (4) is 1 s to 20 s. Specifically, in steps S4 and S5, the carrier gas is an inert gas, such as nitrogen or argon, and the flow rate is 10 to 500 mL / min. There is no specific restriction on the time for feeding the niobium source and the sulfur source, as long as sufficient sources can be fed into the reaction chamber, preferably, 0.1-5s; there is no specific restriction on the time for flushing the reaction byproducts and residues of the niobium source and the sulfur source, as long as they can be flushed clean, preferably, 1-20s; the closed reaction chamber is to allow the reaction to proceed fully.

[0020] In a second aspect, an embodiment of the present invention provides a device for preparing an atomic layer deposition niobium disulfide film on a substrate with a large specific surface area, comprising:

[0021] Source path I, source path II, reaction chamber device and vacuum pump (7).

[0022] The source path I is used to transport the Nb source to the reaction chamber device, and the source path I includes a Nb source (17), a manual valve V1 (16), a pneumatic valve V11 (12), a flow meter 1 (19), a source path I pressure sensor P1 (20) and a multi-heating range collaborative heating system;

[0023] The source path II is used to deliver S source to the reaction chamber device, and the source path II comprises: S source (11), manual valve V2 (10), pneumatic valve V22 (9), source path II pressure sensor P2 (8) and flow meter 2 (13).

[0024] Specifically, the heating device of the multi-heating range collaborative heating system includes: a solid source heating device 1 (1), a solid source heating device 2 (14), a solid source heating device 3 (15) and a solid source heating device 4 (18), wherein the upper computer is connected to the controller, the controller is connected to the solid-state relay, and the solid-state relay is connected to the solid source heating device 1 (1), the solid source heating device 2 (14), the solid source heating device 3 (15) and the solid source heating device 4 (18); the multi-heating range collaborative heating system also includes a temperature sensor for collecting the heating temperatures of the solid source heating device 1 (1), the solid source heating device 2 (14), the solid source heating device 3 (15) and the solid source heating device 4 (18), and the temperature sensor transmits the collected temperature data to the collection device;

[0025] The solid source heating device 1 (1) is installed close to the pipeline from the pneumatic valve V11 (12) to the reaction chamber (4), and the heating range of the solid source heating device 1 (1) is used as a first heating range, and the heating range of the first heating range at least covers the pipeline from the pneumatic valve V11 (12) to the reaction chamber (4);

[0026] The solid source heating device 2 (14) is installed close to the pneumatic valve V11 (12), and the heating range of the solid source heating device 2 (14) serves as a second heating range, and the heating range of the second heating range at least covers the pneumatic valve V11 (12);

[0027] The solid source heating device 3 (15) is installed close to the manual valve V1 (16), and the heating range of the solid source heating device 3 (15) serves as a third heating range, and the heating range of the third heating range at least covers the manual valve V1 (16);

[0028] The solid source heating device 4 (18) is installed close to the Nb source bottle (17), and the heating range of the solid source heating device 4 (18) serves as a fourth heating range, and the heating range of the fourth heating range at least covers the Nb source bottle (17).

[0029] Specifically, the reaction chamber device comprises a pneumatic valve V3 (2), a chamber pressure sensor P0 (3), a reaction chamber (4), a chamber heating device (5) and a pneumatic valve V4 (6);

[0030] The pneumatic valve V3 (2) and the pneumatic valve V4 (6) are respectively linked with the pneumatic valve V11 (12) and the pneumatic valve V22 (9) in the source path I and the source path II. During the linked control, when the niobium source is fed into the reaction chamber (4), the pneumatic valve V3 (2) is closed.

[0031] After the sulfur source is fed into the reaction chamber (4), the pneumatic valve V4 (6) is closed.

[0032] The method and device for preparing an atomic layer deposition niobium disulfide film on a substrate with a large specific surface area provided by the embodiment of the present invention can reduce the temperature required for synthesis growth to below 500°C, thereby reducing energy consumption. It can also be directly applied to the deposition growth of thin films on substrates with a large specific surface area, and the process is simple, the film quality is stable, and the thickness is uniform. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 A schematic diagram of a method for atomic layer deposition of niobium disulfide thin films on a substrate with a large specific surface area is provided in an embodiment of the present invention.

[0035] Figure 2 A schematic diagram of a device for atomic layer deposition of niobium disulfide thin films on a substrate with a large specific surface area provided in an embodiment of the present invention.

[0036] Figure 3 This is a SEM image of the niobium disulfide film prepared by the present invention. The substrate is a carbon fiber paper with a large specific surface area structure. In the figure, (a) is bare carbon fiber paper, and (bf) are niobium disulfide films with 10, 30, 50, 70, and 100 cycles, respectively.

[0037] Figure 4 This is an EDS energy spectrum diagram of the niobium disulfide film prepared by the present invention.

[0038] Figure 5 This is the Raman spectrum of the niobium disulfide film prepared by the present invention. From the figure, it can be clearly seen that there are two characteristic peaks E of the niobium disulfide film 1 and E 2 .

[0039] Figure 6 This is the XPS graph of the niobium disulfide film prepared by the method of the present invention, and the Nb peak and S peak signals are obvious.

[0040] Figure 2 The relevant labeled names are as follows: 1. Solid source heating device 1; 2. Pneumatic valve V3; 3. Cavity pressure sensor P0; 4. Reaction chamber; 5. Cavity heating device; 6. Pneumatic valve V4; 7. Vacuum pump; 8. Source path II pressure sensor P2; 9. Pneumatic valve V22; 10. Manual valve V2; 11. S source; 12. Pneumatic valve V11; 13. Flow meter 2; 14. Solid source heating device 2; 15. Solid source heating device 3; 16. Manual valve V1; 17. Nb source; 18. Solid source heating device 4; 19. Flow meter 1; 20. Source path I pressure sensor P1. DETAILED DESCRIPTION

[0041] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. The embodiments of the present invention will be described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and cannot be interpreted as limiting the present invention. It can be understood by those skilled in the art that, unless specifically stated, the singular forms "one", "one", "said" and "the" used herein may also include plural forms. It should be further understood that the term "including" used in the specification of the present invention refers to the presence of the features, integers, steps, operations, elements and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or their groups. It should be understood that when we say that an element is "connected" or "coupled" to another element, it can be directly connected or coupled to other elements, or there may also be intermediate elements. In addition, the "connection" or "coupling" used here may include wireless connection or coupling. The term "and / or" used herein includes any unit and all combinations of one or more associated listed items. It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical terms and scientific terms) used herein have the same meaning as generally understood by those of ordinary skill in the art to which the present invention belongs. It should also be understood that terms such as those defined in general dictionaries should be understood to have meanings consistent with the meanings in the context of the prior art, and will not be interpreted with idealized or overly formal meanings unless defined as herein.

[0042] Existing technical methods include hydrothermal synthesis and chemical vapor deposition (CVD). Although large-area, high-quality niobium disulfide can be obtained, there are some shortcomings: (1) The synthesis growth temperature is relatively high, requiring 650℃-1000℃, which limits the application on substrates that are not resistant to high temperatures. The high-temperature preparation environment also leads to high energy consumption in the preparation process, and the cost in large-scale preparation processes is difficult to control; (2) Since the growth process is continuous, the thickness of the film is not easy to accurately control; (3) For structures with high aspect ratios and large specific surface areas, such as holes, grooves and meshes, the CVD method cannot deposit uniform films, and the material will be deposited at the open edges. Therefore, the chemical vapor deposition method is not suitable for depositing niobium disulfide on electrode surfaces with large specific surface areas.

[0043] The atomic layer deposition process (ALD) relies on the self-limiting chemical reaction of the precursor on the surface of the substrate sample to deposit a thin film. By alternately introducing precursor pulses, atomic layer deposition can uniformly deposit thin films on structures with high aspect ratios, and the thickness of the film can be precisely controlled by controlling the number of cycles. Since the deposition temperature is low, there is no requirement for the high temperature resistance of the substrate. Therefore, this embodiment uses atomic layer deposition to deposit niobium disulfide on the surface of a substrate with a large specific surface area. The specific implementation is the following embodiment.

[0044] Example 1: A method for atomic layer deposition of niobium disulfide thin film on a substrate with a large specific surface area, combined with Figure 1 , the method comprises the following steps:

[0045] Step S1, placing the substrate in a plasma cleaning machine for treatment to enhance its surface energy and functionalize its surface active groups;

[0046] Step S2, the processed substrate is placed in the reaction chamber, the vacuum system evacuates the reaction chamber and pipelines to maintain a certain vacuum degree, and the reaction chamber is heated;

[0047] Step S3, loading the niobium Nb source into a source bottle, and using multi-temperature zone coordinated heating to heat the niobium source and the delivery pipeline respectively;

[0048] Step S4, using a carrier gas to deliver the niobium source into a reaction chamber with a substrate, sealing the reaction chamber, allowing the niobium source to fully undergo self-limiting chemical adsorption with active functional groups on the surface of the substrate, forming a chemical functional group layer containing niobium on the substrate, connecting the reaction chamber, and continuing to introduce carrier gas to wash away reaction byproducts and residual niobium source;

[0049] Step S5, using a carrier gas to deliver a sulfur source into a reaction chamber containing a substrate, sealing the reaction chamber, allowing the sulfur source to fully undergo a self-limiting chemical reaction with the niobium layer formed in step S4, generating a niobium disulfide atomic layer on the substrate, connecting the reaction chamber, and continuing to introduce a carrier gas to flush out reaction byproducts and residual sulfur source;

[0050] Step S6, repeating steps S4 and S5 according to the required thickness of the niobium disulfide film. Steps S4 and S5 include two self-limiting chemical reactions, forming a complete niobium disulfide atomic layer deposition cycle. The number of cycles of steps S5 and S6 is controlled to control the thickness of the final deposited niobium disulfide film.

[0051] In step S1, the functionalization is hydroxylation or thiolation.

[0052] In step S2, the substrate is a substrate with a large specific surface area, such as carbon fiber paper, nickel metal foam, etc. It is very difficult to deposit a niobium disulfide film on the surface of such a substrate with a large specific surface area by conventional methods. The present invention relies on the self-limiting chemical reaction of the precursor on the surface of the substrate sample to deposit the film, and can uniformly deposit the niobium disulfide film on a large specific surface area structure with a high aspect ratio; the vacuum degree is not specifically required as long as it can meet the atomic layer deposition process, preferably, it is controlled at 1 to 1000 Pa; the specific heating temperature of the heating reaction chamber is determined according to the specific niobium source and sulfur source, preferably, it is controlled at 200-500 degrees Celsius.

[0053] In step S3, the niobium source Nb needs to have self-limiting chemical reaction ability, and can be selected from niobium organic metals or tantalum halides, such as niobium hexacarbonyl, niobium fluoride, niobium chloride, etc. These niobium sources are usually solid, and their saturated vapor pressure at room temperature is low. In order to ensure sufficient delivery and sufficient reaction on the surface of the substrate with a large specific surface area, it is necessary to heat them. However, when the heated niobium source vapor flows through manual valves, pneumatic valves and other components, the solution condenses and blocks. Therefore, the present invention adopts a multi-temperature zone coordinated heating method to heat the niobium source and pipeline components respectively, so that the delivery pipeline from the source bottle to the cavity forms a temperature increasing distribution, thereby avoiding blockage and providing a sufficient amount.

[0054] In steps S4 and S5, the carrier gas is an inert gas, such as nitrogen or argon, and the flow rate is 10 to 500 mL / min. There is no specific restriction on the time for feeding the niobium source and the sulfur source, as long as sufficient sources can be fed into the reaction chamber, preferably 0.1 to 5 seconds; there is no specific restriction on the time for flushing the reaction byproducts and residues of the niobium source and the sulfur source, as long as they can be flushed clean, preferably 1 to 20 seconds; the closed reaction chamber is to allow the reaction to proceed fully, and there is no specific restriction on the closed time, as long as the reaction can proceed fully, preferably, in this embodiment, the closed time is set in the range of 1 second to 30 seconds.

[0055] In step S5, the sulfur source needs to have self-limiting chemical reaction capability, and can be selected from hydrogen sulfide, dialkyl disulfide, dihalogenated disulfide, mercapto-containing organic matter and plasma thereof.

[0056] The preparation method includes two self-limiting chemical reactions, which constitute a complete cycle. By controlling the number of cycles, the thickness of the grown niobium disulfide film can be precisely controlled.

[0057] The substrates that can be deposited by the present invention are not limited to complex substrates with large specific surface areas. Atomic layer deposition of niobium disulfide films can also be performed on simpler planar substrates, such as silicon oxide, sapphire, silicon wafers and the like.

[0058] Embodiment 2: A device for atomic layer deposition of niobium disulfide thin film on a substrate with a large specific surface area, such as Figure 2 As shown, the device comprises: a source path I, a source path II, a reaction chamber device, and a vacuum pump (7).

[0059] The source path I is used to transport the Nb source to the reaction chamber device, and is composed of a Nb source (17), a manual valve V1 (16), a pneumatic valve V11 (12), a flow meter 1 (19), a source path I pressure sensor P1 (20), and a multi-temperature zone coordinated solid source transport device.

[0060] The multi-temperature zone coordinated solid source conveying device is composed of a host computer, a controller, a solid-state relay, a solid source heating device 1 (1), a solid source heating device 2 (14), a solid source heating device 3 (15), a solid source heating device 4 (18), a temperature sensor, and a collection device. The multi-temperature zone coordinated solid source conveying device can realize the coordinated control of four temperature zones of the Nb source (17), the manual valve V1 (16), the pneumatic valve V11 (12), and the pipeline, forming a multi-temperature gradient Nb source conveying, so as to improve the accuracy of the solid Nb source conveying amount, reduce the condensation phenomenon of the valve body and the pipeline, increase the service life of the components, and reduce the use cost. The working process is as follows: according to the requirements of the atomic layer deposition process, the heating temperatures of the four solid source heating devices are preset on the host computer, and then the host computer transmits the heating temperature parameters to the controller. The controller controls the four solid source heating devices to heat according to the preset temperature through the solid-state relay. The acquisition device feeds back the temperatures (T1, T2, T3, T4) and pipeline pressure (P1) of the four solid source heating devices to the controller through the temperature sensor and the source path I pressure sensor P1 (21), thus forming a closed-loop control.

[0061] The source path II is composed of an S source (11), a manual valve V2 (10), a pneumatic valve V22 (9), a source path II pressure sensor P2 (8), and a flow meter 2 (13), and is used to transport the S source for atomic layer deposition of niobium disulfide thin film to a reaction chamber device.

[0062] The reaction chamber device is composed of a pneumatic valve V3 (2), a chamber pressure sensor P0 (3), a reaction chamber (4), a chamber heating device (5), and a pneumatic valve V4 (6), and is used for atomic layer deposition reaction of niobium disulfide thin films on large-area substrates.

[0063] The pneumatic valve V3 (2) and the pneumatic valve V4 (6) are linked with the pneumatic valve V11 (12) and the pneumatic valve V22 (9) in the source path I and the source path II to ensure that the pneumatic valve V3 (2) and the pneumatic valve V4 (6) are closed in time after the niobium source and the sulfur source are fed into the reaction chamber, so that the niobium source and the sulfur source can fully react in the chamber.

[0064] The vacuum pump (7) is used to provide vacuum to the system.

[0065] Embodiment 3: In the practical application of this embodiment, some relatively preferred solutions are also explored and designed. For example, in the practical application, nitrogen is used as the carrier gas, and niobium pentachloride NbCl is used as the Nb source and the S source respectively. 5 and hydrogen sulfide H 2 S, carbon fiber paper is used as the substrate for large area comparison, and atomic layer deposition of niobium disulfide film is carried out. Figure 1 and Figure 2 , the above process steps can be further described in detail:

[0066] Step S1, placing the carbon fiber paper substrate in a plasma cleaning machine for treatment to enhance its surface energy and hydroxylate its surface;

[0067] Step S2, the treated carbon fiber paper substrate is placed in the reaction chamber (4), the vacuum pump (7) evacuates the reaction chamber (4) and the pipeline to maintain a pressure of 800 Pa, and the chamber heating device (5) heats the reaction chamber (4) to 450 degrees Celsius and maintains the temperature;

[0068] Step S3, the niobium Nb source (17) NbCl 5 The source bottle is loaded, and the niobium source and the conveying pipeline are heated respectively by multi-temperature zone coordinated heating, wherein the heating temperatures of the niobium source (17), the manual valve V1 (16), the pneumatic valve V11 (12), and the conveying pipeline are 140, 160, 180, and 200 degrees Celsius, respectively;

[0069] Step S4, open the manual valve V1 (16), open the pneumatic valve V11 (12) for 1 second, and use the carrier gas nitrogen to transfer the niobium source NbCl 5 The carbon fiber paper substrate is placed in the reaction chamber (4), the flow meter 2 (13) sets the carrier gas flow rate at 100 sccm, the pneumatic valve V3 (2) and the pneumatic valve V4 (6) are closed, and the reaction chamber (4) is sealed to make NbCl 5 The active functional groups hydroxyl groups on the surface of the carbon fiber paper substrate undergo self-limiting chemical adsorption to form a chemical functional group layer containing niobium on the carbon fiber paper substrate. After 5 seconds, the pneumatic valve V3 (2) and the pneumatic valve V4 (6) are opened to connect the reaction chamber (4). The carrier gas nitrogen is continuously introduced for 10 seconds to remove the reaction byproducts and residual NbCl 5 rinse off;

[0070] Step S5, open the manual valve V2, open the pneumatic valve V22 (9) for 1 second, and use the carrier gas nitrogen to transfer the sulfur source H 2 S is sent into the reaction chamber (4) containing the carbon fiber paper substrate, the pneumatic valve V3 (2) and the pneumatic valve V4 (6) are closed, the reaction chamber (4) is sealed, and H 2S and the niobium layer formed in step S4 undergo a self-limiting chemical reaction to form a niobium disulfide atomic layer on the substrate. After 5 seconds, the pneumatic valve V3 (2) and the pneumatic valve V4 (6) are opened to connect the reaction chamber (4), and the carrier gas nitrogen is continuously introduced for 10 seconds to remove the reaction byproducts and residual H 2 S rinse off;

[0071] Step S6, repeating steps S4 and S5 according to the required thickness of the niobium disulfide film. Steps S4 and S5 include two self-limiting chemical reactions, forming a complete niobium disulfide atomic layer deposition cycle. The number of cycles of steps S5 and S6 is controlled to control the thickness of the final deposited niobium disulfide film.

[0072] Steps S4 and S5 were repeated for 10, 30, 50, 70, and 100 cycles, respectively, to obtain 5 groups of niobium disulfide film samples.

[0073] Scanning electron microscope SEM, EDS energy spectrum, Raman spectrum, X-ray photoelectron spectroscopy XPS tests were carried out respectively, and the results are as follows Figure 3 , Figure 4 , Figure 5 , Figure 6 As shown. From scanning electron microscopy data Figure 3 (a), it can be seen that the carbon fiber paper is composed of a large number of carbon fibers, the diameter of the carbon fibers is about 6 microns, and there are a lot of gaps between the carbon fibers. It is very difficult to deposit niobium disulfide on the surface of such porous and large specific surface area carbon fiber structure by conventional methods. Atomic layer deposition is suitable for uniformly depositing materials on the surface of structures with high aspect ratio and large specific surface area due to its special process characteristics. Figure 3 (bf) It can be seen that NbS 2 It is uniformly deposited on the surface of the carbon fiber, and the amount of deposition increases with the increase in the number of cycles. From the EDS spectrum, it can be seen that the S / Nb ratio of the deposited niobium disulfide film is close to 2. From the Raman spectrum data, it can be clearly seen that the characteristic peak E 1 and E 2 From the X-ray photoelectron spectroscopy data, it can be seen that the Nb peak and S peak signals are obvious, and the prepared film is indeed a niobium disulfide film.

[0074] Each embodiment in this specification is described in a progressive manner, and the same or similar parts between the embodiments can be referred to each other, and each embodiment focuses on the differences from other embodiments. In particular, for the device embodiment, since it is basically similar to the method embodiment, the description is relatively simple, and the relevant parts can be referred to the partial description of the method embodiment. The above is only a specific implementation method of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or replacements that can be easily thought of by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing an atomic layer deposited niobium disulfide film on a substrate with a large specific surface area, characterized in that: include: Step S1, placing the substrate into a plasma cleaning machine for treatment; Step S2, placing the substrate processed in step S1 into a reaction chamber (4), operating a vacuum pump (7) to evacuate the reaction chamber (4), and then starting a chamber heating device (5) to heat the reaction chamber (4); Step S3, loading the niobium source into the Nb source bottle (17), then starting the multi-heating range collaborative heating system to heat the Nb source bottle (17) and the delivery pipeline between the Nb source bottle (17) and the reaction chamber (4); Step S4, closing the source path II and introducing a carrier gas into the source path I, and using the carrier gas to deliver the niobium source output from the Nb source bottle (17) into the reaction chamber (4), then stopping the introduction of the carrier gas and sealing the reaction chamber (4) until a first reaction time is reached, so that the niobium source and the active functional groups on the surface of the substrate undergo self-limiting chemical adsorption to form a chemical functional group layer containing niobium on the substrate; after the first preset time is reached, introducing the carrier gas into the source path I again and connecting the reaction chamber (4), so that the reaction byproducts and residual niobium source in the reaction chamber (4) are flushed by the carrier gas introduced into the reaction chamber (4) again; Step S5, closing the source path I and introducing a carrier gas into the source path II, and using the carrier gas to deliver the sulfur source output from the S source bottle (11) into the reaction chamber (4), then stopping the introduction of the carrier gas and sealing the reaction chamber (4) until a second reaction time is reached, so that the sulfur source and the niobium layer formed in step S4 undergo a self-limiting chemical reaction, thereby generating a niobium disulfide atomic layer on the substrate, and after the second preset time is reached, introducing a carrier gas into the source path II again and connecting the reaction chamber (4), so that the reaction byproducts and residual sulfur source in the reaction chamber (4) are flushed out by the carrier gas introduced into the reaction chamber (4) again; Step S6, repeating steps S4 to S5 until the thickness of the niobium disulfide film deposited on the surface of the substrate reaches a preset value; The heating temperatures of the niobium Nb source (17), the manual valve V1 (16), the pneumatic valve V11 (12) and the conveying pipeline are 140, 160, 180 and 200 degrees Celsius respectively; The material types for making the substrate include at least carbon fiber paper and nickel metal foam; The substrate has a large specific surface area; The niobium source is niobium hexacarbonyl, niobium fluoride or niobium chloride; the S source is hydrogen sulfide, dialkyl disulfide or dihalogenated disulfide.

2. The method according to claim 1, characterized in that In step S1 , a substrate is placed in a plasma cleaning machine for treatment, so that the surface of the substrate is functionalized, wherein the functionalization includes hydroxylation or thiolization.

3. The method according to claim 1, characterized in that In step S2, the vacuum pump (7) evacuates the reaction chamber (4) so ​​that the vacuum degree of the reaction chamber (4) is maintained in a range greater than or equal to 1 and less than or equal to 1000 Pa; The cavity heating device (5) heats the reaction cavity (4) to a temperature T5, where T5∈[200°C, 500°C].

4. The method according to claim 1, characterized in that: The carrier gas flow rate is 10 mL / min to 500 mL / min; In step S4, the niobium source output from the Nb source bottle (17) is sent into the reaction chamber (4) by using a carrier gas for a time period of 0.1s to 5s; The time for flushing the reaction chamber (4) with the carrier gas introduced into the reaction chamber (4) again is 1 second to 20 seconds; In step S5, the sulfur source output from the S source bottle (17) is sent into the reaction chamber (4) by using a carrier gas for a time period of 0.1s to 5s; The time length for flushing the reaction chamber (4) with the carrier gas introduced into the reaction chamber (4) again is 1 second to 20 seconds.

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