A reaction chamber structure for preparing borophene by chemical vapor deposition and a manufacturing method thereof

Abstract

The present invention is a reaction chamber structure for preparing borophene by chemical vapor deposition and a method for making the same, and belongs to the technical field of two-dimensional thin film preparation. The reaction chamber structure of the present invention comprises a first corundum cylindrical tube, in which a reaction device and a deposition device are arranged, the reaction device adopts a corundum boat, and the deposition device comprises a second corundum cylindrical tube, in which a self-supporting superimposed structure is arranged, and the self-supporting superimposed structure is composed of a lower substrate, a middle substrate and an upper substrate. The reaction chamber structure of the present invention is scientifically designed, ingeniously structured, simple to make and easy to use, and achieves the purpose of directly and effectively increasing the yield of borophene without adding other supports or auxiliary conditions. Borophene is prepared by the reaction chamber structure of the present invention, and eventually large-sized borophene sheets can be prepared on three-layer substrates, and the borophene morphology structures on the lower substrate, the middle substrate and the upper substrate are consistent.

Description

Technical Field

[0001] The invention belongs to the technical field of two-dimensional film preparation, and in particular is a reaction chamber structure for preparing borophene by chemical vapor deposition and a manufacturing method thereof. Background Art

[0002] Since 2004, the rise of graphene has aroused great interest in the principles, preparation and application of two-dimensional thin film materials in the scientific and business communities. Among them, two-dimensional boron materials (borophene) have attracted widespread attention from the scientific community due to their special structural complexity and remarkable physical and chemical properties. Chemical vapor deposition is a common method for preparing two-dimensional thin film materials. In recent years, it has been widely used in the preparation of borophene materials. Its tubular furnace reaction chamber is generally divided into a reaction zone and a deposition zone. The principle of chemical vapor deposition is to use airflow to transport the gaseous precursor in the reaction zone to the deposition zone. After the chemical reaction between atoms and molecules, some chemical bonds of the gaseous precursor are broken, the molecules are decomposed into atoms, and some atoms and atomic groups are adsorbed on the substrate surface, diffuse and migrate, collide and combine with each other, and finally form a thin film. In short, two or more gaseous precursors in the reaction zone undergo chemical reactions to form a new gaseous material, which is finally deposited on the substrate surface in the deposition zone.

[0003] But in fact, the reaction in the reaction chamber is very complicated and is affected by many necessary factors, such as gas flow rate, precursor ratio, substrate temperature, gas flow path, etc. Therefore, the overall structural design of the reaction chamber is very important. Summary of the invention

[0004] The purpose of the present invention is to provide a newly designed reaction chamber structure for preparing borophene by chemical vapor deposition, which does not require support assistance, does not affect the overall airflow environment of the reaction chamber, and can significantly increase the yield of two-dimensional thin film materials.

[0005] The present invention is achieved through the following technical solutions:

[0006] A reaction chamber structure for preparing borophene by chemical vapor deposition, characterized in that: it comprises a first corundum cylindrical tube, one end of the first corundum cylindrical tube is set as a reaction zone, and the other end is set as a deposition zone, a reaction device is set at the reaction zone, and a deposition device is set at the deposition zone;

[0007] The reaction device uses a corundum boat, and the height of the corundum boat is smaller than the inner diameter of the first corundum cylindrical tube;

[0008] The deposition device includes a second corundum cylindrical tube, the length and diameter of the second corundum cylindrical tube are smaller than the length and diameter of the first corundum cylindrical tube, and the axial direction of the second corundum cylindrical tube is consistent with the axial direction of the first corundum cylindrical tube; a self-supporting superimposed structure is arranged in the middle position inside the second corundum cylindrical tube, and the self-supporting superimposed structure is composed of a lower substrate, a middle substrate and an upper substrate, the lower substrate is an arc-shaped substrate bending downward, the middle substrate is a horizontally arranged straight substrate, and the upper substrate is an arc-shaped substrate bending upward, and the curvature of the lower substrate and the upper substrate is consistent with the curvature of the inner tube wall of the second corundum cylindrical tube; the overall height of the self-supporting superimposed structure is smaller than the inner diameter of the second corundum cylindrical tube.

[0009] Preferably, the self-supporting stacked structure is made of metal material.

[0010] Preferably, the metal material includes nickel foam, copper foam, or nickel foil.

[0011] Preferably, the diameter of the first corundum cylindrical tube is Φ50-Φ70 mm, the diameter of the second corundum cylindrical tube is Φ30-Φ50 mm, and the dimensions of the corundum boat are 50×20×10 mm in length, width and height.

[0012] Furthermore, the present invention also provides a method for manufacturing the reaction chamber structure for preparing borophene by chemical vapor deposition, which specifically comprises the following steps:

[0013] 1) Prepare the first corundum cylindrical tube, the corundum boat, the second corundum cylindrical tube and three substrate materials;

[0014] 2) Press a piece of substrate material on the inner wall of the second corundum cylindrical tube by hand to make it fit completely, and then remove it to obtain the lower substrate; press the second substrate material in the same way to obtain the upper substrate; the third substrate material remains straight, which is the middle substrate;

[0015] 3) Aligning and stacking the obtained lower substrate, middle substrate and upper substrate in order from bottom to top to form a self-supporting stacking structure, and placing the self-supporting stacking structure at the middle position inside the second corundum cylindrical tube to form a deposition device as a whole;

[0016] 4) placing the obtained deposition device at the deposition area inside the first corundum cylindrical tube;

[0017] 5) Placing the corundum boat at the reaction zone inside the first corundum cylindrical tube, thus obtaining the reaction chamber structure for preparing borophene by chemical vapor deposition.

[0018] In the reaction chamber structure for preparing borophene by chemical vapor deposition of the present invention, the first corundum cylindrical tube serves as the main body of the reaction chamber, and a reaction zone and a deposition zone are arranged therein. For the preparation of borophene, the precursor is mostly a solid material, so a corundum boat is arranged in the reaction zone as a reaction device, and the corundum boat is loaded with a solid precursor. The height of the corundum boat is much smaller than the inner diameter of the first corundum cylindrical tube, so there is enough space on the upper part of the corundum boat for gas circulation. A deposition device composed of a second corundum cylindrical tube and three layers of substrates is arranged in the deposition zone, and the three layers of substrates are respectively an upper substrate bent upward, a middle substrate placed flat, and a lower substrate bent downward. The second corundum cylindrical tube is used as a container to load the three layers of substrates, and the three layers of substrates are placed in the center position of the second corundum cylindrical tube. The outer diameter of the second corundum cylindrical tube is smaller than the inner diameter of the first corundum cylindrical tube, and the overall height of the three layers of substrates is smaller than the inner diameter of the second corundum cylindrical tube, so the design will not affect the overall airflow environment in the reaction chamber at all.

[0019] As we all know, the temperature zone lengths of different types of CVD tube furnaces have prescribed limits, so increasing the number of substrates in terms of height is a better and more feasible approach. However, if multiple layers of substrates are stacked directly together, the contact area between the substrate and the gas will be reduced, affecting the deposition of boron atoms on the substrate and the overall gas flow environment of the reaction chamber. Metal materials have good ductility and can be bent freely to a certain extent. Upward and downward bending increases the surface area of ​​the substrate. Three pieces of metal material are selected as substrates. The upper substrate is bent upward, the middle substrate is straight, and the lower substrate is bent downward. The three layers are stacked in sequence. The curvature formed by the bending ensures that there is enough gas circulation space between the sheets. The straight substrate of the middle layer plays a key supporting role, connecting the upper and lower substrates to ensure the stability of the structure.

[0020] From the perspective of fluid mechanics, the velocity of gas increases when it flows over the curved surface. For example, the upper and middle basements are It can be inferred that P 上 <P 中 Under the action of pressure difference, B atoms in the gas move to the upper substrate, so that more B atoms are deposited on the upper substrate surface, thereby increasing the yield of borophene. Similarly, more borophene can be deposited on the lower substrate arc surface. In general, this double-arc surface design can not only increase the substrate area, but also control the directional movement of B atoms to the larger arc surface substrate, thereby maximizing the yield of borophene.

[0021] The reaction chamber structure of the present invention is scientifically designed, ingeniously structured, simple to manufacture, and easy to use, achieving the purpose of directly and effectively increasing the yield of borophene without adding other supports or auxiliary conditions. Borophene can be prepared by the reaction chamber structure of the present invention, and eventually a large-sized borophene sheet can be prepared on a three-layer substrate, and the borophene morphology structure on the lower substrate, the middle substrate, and the upper substrate is consistent. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The drawings herein are used to provide further explanation of the present invention and constitute a part of this application. The illustrative embodiments of the present invention and their description are used to explain the present invention and do not constitute improper limitations on the present invention.

[0023] Figure 1 This is a front view of the reaction chamber structure for preparing borophene by chemical vapor deposition according to the present invention.

[0024] Figure 2 A top view of the reaction chamber structure for preparing boroprene by chemical vapor deposition according to the present invention.

[0025] Figure 3 This is a left view of the reaction chamber structure for preparing boroprene by chemical vapor deposition according to the present invention.

[0026] Figure 4 This is a front view of a deposition device in a reaction chamber structure for preparing borophene by chemical vapor deposition according to the present invention.

[0027] Figure 5 A top view of a deposition device in a reaction chamber structure for preparing borophene by chemical vapor deposition according to the present invention.

[0028] Figure 6 This is a left view of a deposition device in a reaction chamber structure for preparing boroprene by chemical vapor deposition according to the present invention.

[0029] Figure 7 This is the SEM image of the borophene material prepared in Inventive Example 1.

[0030] Figure 8 This is the SEM image of the borophene material prepared in Inventive Example 4.

[0031] In the figure: 1-first corundum cylindrical tube, 2-reaction device, 3-deposition device, 4-second corundum cylindrical tube, 5-self-supporting superposition structure, 6-solid precursor material, a-upper substrate, b-middle substrate, c-lower substrate. Implementation

[0032] In order to make those skilled in the art better understand the present invention, the present invention is further clearly and completely described below in conjunction with the accompanying drawings and embodiments. It should be noted that, in the absence of conflict, the features in the embodiments and examples of this application can be combined with each other.

[0033] In the description of the present invention, it is necessary to understand that the orientations or positional relationships indicated by the terms "upper", "middle", "lower", etc. are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0034] A reaction chamber structure for preparing boronene by chemical vapor deposition, such as Figures 1 to 3 As shown, it includes a first corundum cylindrical tube 1, the diameter range of the first corundum cylindrical tube 1 is Φ50-Φ70mm, one end of the first corundum cylindrical tube 1 is set as a reaction zone, and the other end is set as a deposition zone, a reaction device 2 is set at the reaction zone, and a deposition device 3 is set at the deposition zone.

[0035] The reaction device 2 uses a corundum boat, the height of the corundum boat is smaller than the inner diameter of the first corundum cylindrical tube 1, and the size of the corundum boat can be selected to be 50×20×10 mm.

[0036] The structure of the deposition device 3 is as follows: Figures 4 to 6 As shown, it includes a second corundum cylindrical tube 4, the length and diameter of the second corundum cylindrical tube 4 are smaller than the length and diameter of the first corundum cylindrical tube 1, the diameter range of the second corundum cylindrical tube 4 is Ф30-Ф50mm, and the axial direction of the second corundum cylindrical tube 4 is consistent with the axial direction of the first corundum cylindrical tube 1; a self-supporting superimposed structure 5 is arranged in the middle position inside the second corundum cylindrical tube 4, the self-supporting superimposed structure 5 is composed of a lower substrate c, a middle substrate b and an upper substrate a, the lower substrate c is an arc-shaped substrate bent downward, the middle substrate b is a horizontally arranged straight substrate, and the upper substrate a is an arc-shaped substrate bent upward, and the curvature of the lower substrate c and the upper substrate a is consistent with the curvature of the inner tube wall of the second corundum cylindrical tube 4; the overall height of the self-supporting superimposed structure 5 is smaller than the inner diameter of the second corundum cylindrical tube 4, and the self-supporting superimposed structure 5 can be made of metal materials, and the metal materials include foamed nickel, foamed copper, and nickel foil.

[0037] The technical solution of the present invention is further described below in conjunction with several specific embodiments. Example

[0038] A method for manufacturing a reaction chamber structure for preparing borophene by chemical vapor deposition comprises the following steps:

[0039] 1) Press a 40×20 mm nickel foam onto the inner tube wall of a second corundum cylindrical tube 4 with a diameter of 30 mm by hand to make it completely fit, and remove it to obtain a lower substrate c; press another piece of nickel foam of the same size in the same way to obtain an upper substrate a; and take another flat piece of nickel foam as a middle substrate b;

[0040] 2) Align and stack the downwardly curved lower substrate c, the straight middle substrate b, and the upwardly curved upper substrate a in order from bottom to top to form a self-supporting stacking structure 5, and place the self-supporting stacking structure 5 at the middle position inside the second corundum cylindrical tube 4 to form a deposition device 3 as a whole;

[0041] 3) placing the obtained deposition device 3 at the deposition area inside the first corundum cylindrical tube 1 with a diameter of 50 mm;

[0042] 4) A corundum boat with a size of 50×20×10 mm is placed at the reaction zone inside the first corundum cylindrical tube 1 with a diameter of Φ50 mm, thereby obtaining the reaction chamber structure for preparing borophene by chemical vapor deposition.

[0043] Borophene material was prepared by using the reaction chamber structure prepared above. 200 mg of solid precursor material 6 was loaded into a corundum boat. Borophene material was prepared through reaction. The SEM image of the borophene material is shown in FIG. Figure 7 As shown in the figure, it can be seen that a large number of micron-sized boron olefin sheets are deposited on the surface of nickel foam. From the high-magnification scanning electron microscope image, it is observed that the boron olefin sheets on the three layers of nickel foam are all ultra-thin and transparent, and the thickness, width and length of these boron olefin sheets are all in the same order of magnitude. The results verify that the morphology and structure of the boron olefin deposited on the three layers of nickel foam, namely the lower substrate c, the middle substrate b and the upper substrate a, are consistent, and the self-supporting substrate increases the yield of boron olefin. Example

[0044] A method for manufacturing a reaction chamber structure for preparing borophene by chemical vapor deposition comprises the following steps:

[0045] 1) Press a 50×30 mm nickel foil by hand onto the inner tube wall of the second corundum cylindrical tube 4 with a diameter of 40 mm to make it completely fit, and remove it to obtain the lower substrate c; press another piece of nickel foil of the same size in the same way to obtain the upper substrate a; and take another flat nickel foil as the middle substrate b;

[0046] 2) Align and stack the downwardly curved lower substrate c, the straight middle substrate b, and the upwardly curved upper substrate a in order from bottom to top to form a self-supporting stacking structure 5, and place the self-supporting stacking structure 5 at the middle position inside the second corundum cylindrical tube 4 to form a deposition device 3 as a whole;

[0047] 3) placing the obtained deposition device 3 at the deposition area inside the first corundum cylindrical tube 1 with a diameter of 60 mm;

[0048] 4) A corundum boat with a size of 50×20×10 mm is placed at the reaction zone inside the first corundum cylindrical tube 1 with a diameter of 60 mm, thereby obtaining the reaction chamber structure for preparing borophene by chemical vapor deposition.

[0049] Borophene material is prepared by using the reaction chamber structure prepared above. 300 mg of solid precursor material 6 is loaded into a corundum boat, and the borophene material is prepared through reaction. Example

[0050] A method for manufacturing a reaction chamber structure for preparing borophene by chemical vapor deposition comprises the following steps:

[0051] 1) Press the 60×40mm copper foam by hand on the inner tube wall of the second corundum cylindrical tube 4 with a diameter of 50mm to make it fit completely, and then remove it to obtain the lower substrate c; press another piece of copper foam of the same size in the same way to obtain the upper substrate a; and take another flat piece of copper foam as the middle substrate b;

[0052] 2) Align and stack the downwardly curved lower substrate c, the straight middle substrate b, and the upwardly curved upper substrate a in order from bottom to top to form a self-supporting stacking structure 5, and place the self-supporting stacking structure 5 at the middle position inside the second corundum cylindrical tube 4 to form a deposition device 3 as a whole;

[0053] 3) placing the obtained deposition device 3 at the deposition area inside the first corundum cylindrical tube 1 with a diameter of 70 mm;

[0054] 4) A corundum boat with a size of 50×20×10 mm is placed at the reaction zone inside the first corundum cylindrical tube 1 with a diameter of 70 mm, thereby obtaining the reaction chamber structure for preparing borophene by chemical vapor deposition.

[0055] Borophene material is prepared by using the reaction chamber structure prepared above. 400 mg of solid precursor material 6 is loaded into a corundum boat, and the borophene material is prepared through reaction. Example

[0056] A method for manufacturing a reaction chamber structure for preparing borophene by chemical vapor deposition comprises the following steps:

[0057] 1) Press a 40×20 mm nickel foam onto the inner tube wall of a second corundum cylindrical tube 4 with a diameter of 30 mm by hand to make it completely fit, and remove it to obtain a lower substrate c; press another piece of nickel foam of the same size in the same way to obtain an upper substrate a; and take another flat piece of nickel foam as a middle substrate b;

[0058] 2) Align and stack the downwardly curved lower substrate c, the straight middle substrate b, and the upwardly curved upper substrate a in order from bottom to top to form a self-supporting stacking structure 5, and place the self-supporting stacking structure 5 at the middle position inside the second corundum cylindrical tube 4 to form a deposition device 3 as a whole;

[0059] 3) placing the obtained deposition device 3 at the deposition area inside the first corundum cylindrical tube 1 with a diameter of 50 mm;

[0060] 4) A corundum boat with a size of 50×20×10 mm is placed at the reaction zone inside the first corundum cylindrical tube 1, thereby obtaining the reaction chamber structure for preparing borophene by chemical vapor deposition.

[0061] Borophene material was prepared by using the reaction chamber structure prepared above. 600 mg of solid precursor material 6 was loaded into a corundum boat. Borophene material was prepared through reaction. The SEM image of the borophene material is shown in FIG. Figure 8 As shown in the figure, a large number of layered micron-sized boron olefin sheets are deposited on the surface of nickel foam. From the high-power scanning electron microscope image, it is observed that these polygonal boron olefin sheets are stacked together in a terraced shape with sharp edges. The overall boron olefin morphology structure of the three layers of nickel foam, namely the lower substrate c, the middle substrate b and the upper substrate a, is consistent, and the upper substrate a and the lower substrate c have more boron olefin sheets.

[0062] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A reaction chamber structure for preparing boronene by chemical vapor deposition, characterized in that: It comprises a first corundum cylindrical tube, one end of the first corundum cylindrical tube is set as a reaction zone, and the other end is set as a deposition zone, a reaction device is set at the reaction zone, and a deposition device is set at the deposition zone; The reaction device uses a corundum boat, and the height of the corundum boat is smaller than the inner diameter of the first corundum cylindrical tube; The deposition device includes a second corundum cylindrical tube, the length and diameter of the second corundum cylindrical tube are smaller than the length and diameter of the first corundum cylindrical tube, and the axial direction of the second corundum cylindrical tube is consistent with the axial direction of the first corundum cylindrical tube; a self-supporting superimposed structure is arranged in the middle position inside the second corundum cylindrical tube, and the self-supporting superimposed structure is composed of a lower substrate, a middle substrate and an upper substrate, the lower substrate is an arc-shaped substrate bending downward, the middle substrate is a horizontally arranged straight substrate, and the upper substrate is an arc-shaped substrate bending upward, and the curvature of the lower substrate and the upper substrate is consistent with the curvature of the inner tube wall of the second corundum cylindrical tube; the overall height of the self-supporting superimposed structure is smaller than the inner diameter of the second corundum cylindrical tube.

2. The reaction chamber structure for preparing borophene by chemical vapor deposition according to claim 1, characterized in that: The self-supporting superimposed structure is made of metal material.

3. The reaction chamber structure for preparing boropene by chemical vapor deposition according to claim 2, characterized in that: The metal material is nickel foam, copper foam or nickel foil.

4. A reaction chamber structure for preparing borophene by chemical vapor deposition according to any one of claims 1 to 3, characterized in that: The diameter of the first corundum cylindrical tube is Ф50-Ф70 mm, the diameter of the second corundum cylindrical tube is Ф30-Ф50 mm, and the size of the corundum boat is 50×20×10 mm.

5. The method for manufacturing a reaction chamber structure for preparing boroprene by chemical vapor deposition according to claim 1, characterized in that: The steps include: 1) Prepare the first corundum cylindrical tube, the corundum boat, the second corundum cylindrical tube and three substrate materials; 2) Press a piece of substrate material on the inner wall of the second corundum cylindrical tube by hand to make it fit completely, and then remove it to obtain the lower substrate; press the second substrate material in the same way to obtain the upper substrate; the third substrate material remains straight, which is the middle substrate; 3) Aligning and stacking the obtained lower substrate, middle substrate and upper substrate in order from bottom to top to form a self-supporting stacking structure, and placing the self-supporting stacking structure at the middle position inside the second corundum cylindrical tube to form a deposition device as a whole; 4) placing the obtained deposition device at the deposition area inside the first corundum cylindrical tube; 5) Placing the corundum boat at the reaction zone inside the first corundum cylindrical tube, thus obtaining the reaction chamber structure for preparing borophene by chemical vapor deposition.

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