Method for manufacturing carbon nanocone functionalized needle tip

Abstract

The present application provides a carbon nanocone-functionalized needle tip, in which the tip of a needle tip base is decorated with carbon nanocones, the carbon nanocones being cone-shaped carbon nanomaterials with a layered graphite structure, and the material of the needle tip base is one or more metals selected from tungsten, iron, cobalt, nickel, and titanium, the tail ends of the carbon nanocones and the needle tip base form a covalent interface connection, and the orientation of the tips of the carbon nanocones coincides with the orientation of the central axis of the entire needle tip. The present application also provides a method for manufacturing a carbon nanocone-functionalized needle tip. The orientation of the tips of the carbon nanocones coincides with the orientation of the central axis of the entire needle tip, ensuring control of the active emission site of the carbon nanocone tip during electron emission. The manufactured carbon nanocone-functionalized needle tip has a clean and complete graphite layered structure, and the characteristics of the needle tip structure prevent electron emission noise caused by contaminants on the tip surface and damage to the needle tip structure due to uncontrollable emission current, which can lead to failure.

Description

[Technical field]

[0001] The present application relates to the technical field of metal material functionalization, in particular to carbon nanocone functionalized needles Previous It relates to a manufacturing method. [Background technology]

[0002] Electron emission sources are core components of vacuum electronic devices and are widely used in fields such as X-ray sources, microwave sources, ionization chambers of mass spectrometers, field emission displays, etc. Among them, electron sources with high brightness and large beam current can be used as light sources for electron microscopes and electron beam exposure devices.

[0003] In recent years, the vigorous development of materials science and nanotechnology has greatly promoted research into new types of electron emission sources (see Non-Patent Documents 1-3). Carbon nanotubes are widely expected to be used in field emission electron sources due to their special structure and properties. Early research results, such as those by De Jonge et al., showed that carbon nanotube needle tips can produce high-brightness, monochromatic electron beams at low deposition voltages (see Non-Patent Documents 4 and 5). However, the manufacturing method of carbon nanotube needle tips has low controllability, and the structure and orientation of the carbon nanotube tips (effective electron emission sites) cannot be ensured, and the physical adhesive bond between the carbon nanotube and the metal W needle tip body is not reliable. These problems have made it impossible to use carbon nanotube needle tips as practical electron guns. In 2016, Zhang et al. of the National Institute for Materials Science, Japan, produced LaB6 single crystal nanowires and characterized their field emission properties, demonstrating excellent electron beam monochromaticity and emission stability (see Non-Patent Document 2). However, like carbon nanotubes, one-dimensional nanowires are difficult to ensure the orientation of the nanowire tip and the mechanical and electrical properties of the interface structure between the nanowire and the needle tip body during the fabrication of the assembly to the metal needle tip body. In 2018, Khursheed's group at the National University of Singapore used chemical vapor deposition to grow graphene on the surface of a Ni needle tip and demonstrated the extremely low surface work function and high electron beam brightness of the functional needle tip (see Non-Patent Document 6). However, since the graphene grown on the tip surface (non-single crystal plane) of the Ni needle tip cannot avoid the presence of a large number of structural defects, the electron emission beam of the functionalized needle tip has low stability and high noise (about 30%). In summary, nanomaterials have provided abundant materials for the development of electron guns, but in order to realize the application of nanomaterial functionalized electron guns, it is necessary to realize precise control of the needle tip fabrication method and ensure the performance of the interface structure, the orientation of the needle tip, and the integrity and cleanness of the tip crystal structure.

[0004] The manufacturing method of nanomaterial functionalized needle tip is mainly divided into two methods, direct growth method and micro-nano assembly method. The direct growth method is a method of directly synthesizing and growing nanomaterials on the base of the needle tip, but at present, it is not possible to control parameters such as the length, diameter, and orientation of the nanomaterial. The micro-nano assembly method realizes the assembly of a specific nanomaterial and the needle tip base by operating a high-precision three-dimensional manipulation device under a microscope and controlling the precise movement of the probe, and this method has high controllability and is advantageous for controlling the structure and orientation of the nanomaterial. The inventors have manufactured a tapered nanocarbon material functionalized needle tip by using a method that combines micro-nano manipulation and in-situ current heating (see Patent Documents 1 and 2). Compared with the previous nanomaterial functionalized needle tip, this tapered nanocarbon material functionalized needle tip can ensure that the orientation of the nanomaterial needle tip tip is completely consistent with the axial direction of the needle tip base, and the interface between the nanomaterial and the needle tip base has excellent mechanical strength and electrical conductivity.

[0005] As mentioned above, the needle tip of the electron gun must be free of contaminants and structural defects on its surface. Both contaminants and structural defects can cause problems such as uncontrollable electron beam emission, poor stability, and even electron gun failure. During the synthesis, storage, and micro-nano assembly of carbon nanocones, the presence of surface contaminants (mainly amorphous carbon, hydrocarbon compounds, etc.) is unavoidable (see FIG. 1). Therefore, purification of the carbon nanocone needle tip is necessary for application to electron sources. The above published patent documents do not describe a method for purifying the carbon nanocone tip, and conventional purification methods such as air oxidation and wet hydrogen treatment remove contaminants on the surface of the carbon nanocone while simultaneously generating a large number of structural defects (see Non-Patent Document 7). No method has been reported to obtain a clean carbon nanocone needle tip with a perfect tip structure. [Prior art documents] [Patent documents]

[0006]

Patent Document 1

Patent document 2

Non-licensed literature

[0007]

Non-licensed literature 1

Non-licensed Document 2

Non-licensed Document 4

[0008] The present application aims to solve at least one of the technical problems existing in the prior art. [Means for solving the problem]

[0009] To this end, in one aspect, the present application provides a carbon nanocone functionalized needle tip. Manufacturing method Provide The manufacturing method includes step S201 of assembling a carbon nanocone on the tip of a needle tip base, and step S202 of heating the needle tip to a target temperature and introducing an active substance to selectively react with contaminants on the surface of the needle tip to purify the carbon nanocone functionalized needle tip, where the active substance is carbon dioxide or water, and step S202 includes contacting the side of the needle body with another metal body.

[0010] According to one embodiment of the present application, in step S202, both the needle body and the separate metal body are fixed to a micro-nano manipulation arm, and their movements are controlled by the manipulation arm under microscope observation.

[0011] According to one embodiment of the present application, step S202 further includes, when the side of the needle body is brought into contact with the other metal body, applying a continuous current between the needle body and the metal body to locally heat the needle tip to a high temperature and react with the active substance.

[0012] According to one embodiment of the present application, assembling a carbon nanocone on the tip of a needle tip base includes using a micro-nano manipulating arm to control the tip of the needle tip base to enter inside the carbon nanocone, attaching the carbon nanocone to the tip of the needle tip base, contacting the needle tip base with another metal body, applying a voltage between the metal body and the needle tip base, passing a current through the needle tip base, heating the tip portion of the needle tip base and bonding it to the attached carbon nanocone.

[0013] According to one embodiment of the present application, the tip of the needle tip base of the carbon nanocone functionalized needle tip is decorated with a carbon nanocone, the carbon nanocone is a cone-shaped carbon nanomaterial having a layered graphite structure, the material of the needle tip base is one or more metals selected from tungsten, iron, cobalt, nickel and titanium, the tail end of the carbon nanocone and the needle tip base form a covalent interface connection, the orientation of the tip of the carbon nanocone is consistent with the orientation of the central axis of the needle tip, the surface of the tip of the carbon nanocone is clean, and the structure of the graphite layer is complete. Effect of the Invention

[0014] The above-mentioned one or more technical solutions in the embodiments of the present application have at least the following technical effects: By law The carbon nanocone functionalized needle tip obtained thereby provides stable, controllable electron emission of a large beam, enabling application as an electron emission source; a covalent interface connection is realized between the carbon nanocone and the metal needle tip base, and its excellent mechanical strength and electrical conductivity ensure the stability of the carbon nanocone needle tip during the electron emission process; the orientation of the carbon nanocone tip overlaps with the orientation of the central axis of the entire needle tip, ensuring the controllability of the active emission site of the carbon nanocone needle tip during electron emission; and the carbon nanocone functionalized needle tip manufactured in the embodiment of the present application has a carbon nanocone tip with a clean and complete graphite layered structure, and the characteristics of the needle tip structure avoid electron emission noise caused by contaminants on the tip surface and damage to the needle tip structure and even failure due to uncontrollable emission current. [Brief description of the drawings]

[0015] In order to more clearly describe the embodiments of the present application or the technical solutions in the prior art, the drawings necessary for describing the embodiments or the prior art will be briefly described below. Of course, the drawings described below are only some embodiments of the present invention, and those skilled in the art can further obtain other drawings based on these drawings without requiring creative labor. [Figure 1(a)] FIG. 1(a) is a diagram showing the overall structure of a carbon nanocone according to an embodiment of the present application. [Figure 1(b)] FIG. 1(b) is a high-resolution transmission electron micrograph of a carbon nanocone tip according to an embodiment of the present application, showing the layered graphite structure of the carbon nanocone, with the arrows pointing to contaminants on the carbon nanocone surface. [Figure 2(a)] Figure 2(a) is a side view of a metal needle tip attached to a micro-nano manipulation arm in a scanning electron microscope, and the arrows indicate the three micro-nano manipulation arms. [Figure 2(b)] Figure 2(b) is a top view of the metal needle tip attached to the micro-nano manipulation arm in a scanning electron microscope. [Figure 3(a)] FIG. 3(a) is a scanning electron microscope photograph showing the pointed end of a carbon nanocone functionalized needle tip (#1) according to an embodiment of the present application contacting another metal body (#2). [Figure 3(b)] FIG. 3(b) is a transmission electron microscope image of the clean carbon nanocone tip after the electric current treatment. [Figure 4(a)] FIG. 4(a) is a scanning electron microscope photograph showing the side of a carbon nanocone functionalized needle tip (#1) according to an embodiment of the present application in contact with another metal body (#2). [Figure 4(b)] FIG. 4(b) is a transmission electron microscope image of the clean carbon nanocone tip after the electric current treatment. [Figure 4(c)] FIG. 4(c) shows the field emission curve of the fabricated carbon nanocone functionalized needle tip. [Figure 4(d)] Figure 4(d) is an electron micrograph showing a field emission test performed by applying a specific electric field between the carbon nanocone functionalized needle tip (#1) and the anode (#3). [Figure 5(a)] FIG. 5(a) is a scanning electron micrograph of a carbon nanocone functionalized needle tip according to an embodiment of the present application. [Figure 5(b)] FIG. 5(b) is a structural diagram of a clean and complete graphite layer of a carbon nanocone according to an embodiment of the present application. [Figure 6(a)] FIG. 6(a) is a scanning electron micrograph of a carbon nanocone functionalized needle tip according to an embodiment of the present application. [Figure 6(b)] FIG. 6(b) is a structural diagram of a clean and complete graphite layer of a carbon nanocone according to an embodiment of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] In order to make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings. Of course, the described embodiments are not all the embodiments, but only some of the embodiments of the present application. All other embodiments obtained by those skilled in the art without creative work based on the embodiments of the present application are included in the protection scope of the present application.

[0017] FIG. 1(a) is a diagram of the overall structure of a carbon nanocone according to an embodiment of the present application, and FIG. 1(b) is a high-resolution transmission electron microscope image of a carbon nanocone tip according to an embodiment of the present application. As shown in FIG. 1(a) and FIG. 1(b), the present application provides a carbon nanocone functionalized needle tip, in which the tip of a needle base is decorated with a carbon nanocone; The carbon nanocone is a cone-shaped carbon nanomaterial with a layered graphite structure, the material of the needle base is one or more metals selected from tungsten, iron, cobalt, nickel and titanium, the tail end of the carbon nanocone and the needle base form a covalent interface connection, the orientation of the tip of the carbon nanocone is consistent with the orientation of the central axis of the needle tip, the surface of the tip of the carbon nanocone is clean, and the structure of the graphite layer is complete, without any contaminants or damage.

[0018] In another aspect, the present application provides methods for making and cleaning carbon nanocone functionalized needle tips.

[0019] The carbon nanocone and the metal needle tip base are assembled using the method described in published patent ZL201610091160.0. Under an electron microscope, the tip of the metal needle tip base is controlled to enter the inside of the carbon nanocone using a micro-nano operation arm, and the carbon nanocone is attached to the tip of the needle tip base. Then, the needle tip base is brought into contact with another metal body, a voltage is applied between the metal body and the needle tip base, and a current is passed through the needle tip base to heat the tip of the needle and bond it to the attached carbon nanocone. Here, the contact position between the metal body and the needle tip base is 0.2 to 100 μm away from the apex of the needle tip, and the current flowing through the needle body is 0.01 to 5 A.

[0020] The purification method according to the present application is a method for removing contaminants such as amorphous carbon and hydrocarbon compounds from the surface of carbon nanocones by a current flash ablation method or a selective chemical reaction method.

[0021] Fabricating carbon nanocone functionalized needle tips by the current ablation method is Step S101: Assembling a carbon nanocone on the tip of a needle base by combining a micro-nano manipulation method and an in-situ electric current heating method; and step S102 of contacting the needle body with another metal body and applying an instantaneous current between the needle body and the metal body to remove the outer graphite layer of the carbon nanocone together with the contaminants.

[0022] Furthermore, in step S102, both the needle body and the separate metal body are fixed to a micro / nano manipulation arm, and their movements are controlled by the manipulation arm under microscope observation, as shown in FIG. 2(a) and FIG. 2(b).

[0023] Also, step S102 further includes controlling the carbon nanocone tip of the needle body to come into contact with another metal body to form an electric path, and the magnitude of the instantaneous current is 0.01 to 10 mA.

[0024] In addition, in step S102, the side of the needle body is controlled to come into contact with another metal body to form an electrical path, and the contact position between the metal body and the needle body is 0.01 to 1 μm away from the tip of the needle, and the magnitude of the instantaneous current is 1 to 100 mA.

[0025] In one preferred embodiment, the possible mechanism for removing the outer graphite layer of carbon nanocones by a momentary electric current is as follows: Carbon nanocones have a multi-layer graphite structure, and the interlayer resistivity of graphite (10 -3 Ω m) is the layer resistivity (10 -6 Since the electric resistance is 1000 times larger than that of the outer graphite layer (Ω·m), the instantaneous current preferentially passes through the outer graphite layer, causing the carbon-carbon bonds in the layer to break, and the Joule heat generated by the instantaneous current is combined to decompose the outer graphite layer together with the surface contaminants and volatilize them into vacuum, finally obtaining a clean inner graphite layer structure. Furthermore, in this embodiment, step S102 is repeated multiple times to controllably remove a certain number of the outer graphite layers to obtain a clean carbon nanocone functionalized needle tip with a sharper tip.

[0026] The selective chemical reaction method for producing a carbon nanocone functionalized needle tip is Step S201: Assembling a carbon nanocone on the tip of a needle base by using a micro-nano manipulation method and an in-situ electric current heating method; The method includes step S202 of heating the needle tip to a target temperature and introducing an active material to selectively react with contaminants on the surface of the needle tip to purify the carbon nanocone functionalized needle tip, where the active material is a weak oxidizing agent such as carbon dioxide or water.

[0027] Furthermore, in step S202, both the needle body and the separate metal body are fixed to a micro-nano manipulation arm, and their movements are controlled by the manipulation arm under microscope observation, as shown in FIG. 2(a) and FIG. 2(b).

[0028] In step S202, the method further includes contacting the side of the needle body with another metal body contact, applying a continuous current between the needle body and the metal body, locally heating the needle tip to a high temperature, and reacting with the active substance. Preferably, the contact position between the metal body and the needle body is 0.2 to 100 μm away from the apex of the needle tip, and the current flowing through the needle body is 0.01 to 5 A. Carbon dioxide or water vapor is introduced into the sample chamber of the scanning electron microscope using the gas circuit control valve of the environmental scanning electron microscope. The pressure range of the active gas in the sample chamber of the electron microscope is 10 to 2000 Pa.

[0029] In addition, step S202 further includes attaching the needle tip to the needle tip clamping device, placing it in a tube vacuum furnace, introducing carbon dioxide or steam to heat it up to a target temperature, and removing contaminants on the surface of the needle tip. Preferably, the flow rate of carbon dioxide or steam is 100-1000sccm, the heating rate is 1-10℃ / min, the target temperature is 450℃-750℃, and the warming time is 30-600min.

[0030] Specifically, the amorphous carbon and hydrocarbon compound contaminants on the surface of the carbon nanocone have higher chemical reactivity than the graphite structure of the carbon nanocone, and preferentially react with various oxidants to convert them into gas products, thereby achieving the purpose of purifying the surface. In order to remove the surface contaminants while avoiding the introduction of defects into the graphite structure of the carbon nanocone, the technical solution proposed in this application uses mild oxidants such as carbon dioxide and water vapor. Carbon dioxide reacts with the amorphous carbon and hydrocarbon compound contaminants to produce carbon monoxide, and water vapor reacts with the amorphous carbon and hydrocarbon compound contaminants to produce carbon monoxide and hydrogen, and finally obtains a clean carbon nanocone needle tip with a complete graphite structure.

[0031] The technical solution of the present application will be described below using specific embodiments. If no specific techniques or conditions are specified in the embodiments, they shall be carried out according to the techniques or conditions described in the literature in the field or according to the product specifications. Reagents or equipment whose manufacturers are not specified are ordinary products that can be purchased from regular channel vendors.

[0032] In the following specific embodiment, the micro-nano manipulation arm is a product of Kleindiek Nanotechnik, the scanning electron microscope is a Quanta 200 type scanning electron microscope from Thermo Fisher, and the transmission electron microscope is an F20 type transmission electron microscope from Thermo Fisher.

[0033] EMBODIMENT 1 In this embodiment, two tungsten needles are fixed to two micro-nano manipulation arms, and both the micro-nano manipulation arms and the carbon nanocone sample are placed in a scanning electron microscope. First, one tungsten needle (#2) is brought close to the side wall of the metal tungsten needle tip base of #1 at a position 50 μm from the apex of the needle tip base, and an arc is generated by applying a voltage of 60 V between #1 and #2, and the apex of the tungsten needle of #2 is melted into a spherical shape by the arc.

[0034] The tip of needle #1 was inserted into the apex of the selected carbon nanocone, contacted with the carbon nanocone and attached to the apex of the needle tip. Then, the apex of tungsten needle #2 was brought into contact with the side of the tungsten needle tip (#1), and the contact position was 2 μm away from the apex of needle tip #1. A voltage was applied to the two tungsten needle tips to generate a current of 2 A. The current flow duration was 0.1 ms, and the apex of the metal tungsten needle tip (#1) melted, and the molten metal tungsten automatically entered and filled the internal space of the carbon nanocone, resulting in the functionalized needle tip #1 as shown in Figure 3(a).

[0035] The functionalized carbon nanocone tip (#1) was moved so that its tip contacted the apex of the tungsten needle (#2), and an instantaneous current of 1 mA was applied for 0.5 μs. After the current was turned off, the carbon nanocone tip was quickly removed while avoiding the electron beam irradiation on the tip surface. The morphology of the removed carbon nanocone tip was observed under a transmission electron microscope, and a clean tip without any damaged graphite layer was obtained, as shown in Figure 3(b).

[0036] EMBODIMENT 2 In this embodiment, two tungsten needles are fixed to two micro-nano manipulation arms, and both the micro-nano manipulation arms and the carbon nanocone sample are placed in a scanning electron microscope. First, one tungsten needle (#2) is brought close to the side wall of the metal tungsten needle tip base of #1 at a position 50 μm from the apex of the needle tip, and a voltage of 60 V is applied between #1 and #2 to generate an arc, which melts the apex of the tungsten needle of #2 into a spherical shape.

[0037] The tip of the needle #1 was inserted into the apex of the selected carbon nanocone, contacted with the carbon nanocone and attached to the apex of the needle tip. Then, the apex of the tungsten needle #2 was brought into contact with the side of the tungsten needle tip (#1), and the contact position was 3 μm away from the apex of the needle tip #1. A voltage was applied to the two tungsten needle tips to generate a current of 3 A. The current flow duration was 0.1 ms, and the apex of the metal tungsten needle tip (#1) melted, and the molten metal tungsten automatically entered and filled the internal space of the carbon nanocone, resulting in the functionalized needle tip #1 as shown in Figure 4(a).

[0038] The functionalized carbon nanocone tip #1 was moved so that the side of the carbon nanocone was brought into contact with the sphere at the top of the tungsten needle #2, and an instantaneous current of 20 mA was applied for 0.5 μs. After the current was turned off, the carbon nanocone tip #1 was quickly removed while avoiding the electron beam irradiation on the tip surface. The morphology of the removed carbon nanocone tip was observed under a transmission electron microscope, and a clean tip without any damaged graphite layer was obtained, as shown in Figure 4(b).

[0039] As shown in Figure 4(d), using the driving device in the sample rod of the in situ transmission electron microscope, the carbon nanocone functionalized needle tip #1 is moved so that the distance from the surface of the Au electrode #3 is about 500 nm. When a continuously changing voltage (40-200 V) is applied between the Au electrode (anode) and the carbon nanocone functionalized needle tip (cathode) and the corresponding current is recorded, a field emission curve as shown in Figure 4(c) is obtained. From this, it can be seen that the carbon nanocone functionalized needle tip manufactured by the present invention can provide a large beam emission of 100 μA.

[0040] EMBODIMENT 3 In this embodiment, two tungsten needles are fixed to two micro-nano manipulation arms, and both the micro-nano manipulation arms and the carbon nanocone sample are placed in a scanning electron microscope. First, one tungsten needle (#2) is brought close to the side wall of the metal tungsten needle tip base of #1 at a position 50 μm from the apex of the needle tip base, and an arc is generated by applying a voltage of 60 V between #1 and #2, and the apex of the tungsten needle of #2 is melted into a spherical shape by the arc.

[0041] The tip of needle #1 was inserted into the apex of the selected carbon nanocone, contacted with the carbon nanocone and attached to the apex of the needle tip. Then, the apex of tungsten needle #2 was brought into contact with the side of the tungsten needle tip (#1), and the contact position was 3 μm away from the apex of needle tip #1. A voltage was applied to the two tungsten needle tips to generate a current of 3 A. The current flow duration was 0.1 ms, and the apex of the metal tungsten needle tip (#1) melted, and the molten metal tungsten automatically entered and filled the internal space of the carbon nanocone, resulting in a carbon nanocone functionalized needle tip as shown in Figure 5(a).

[0042] The electron microscope mode was switched to the environmental scanning electron microscope mode, a carbon dioxide atmosphere was introduced, and the pressure of the carbon dioxide in the sample chamber was controlled to 1000 Pa by the pressure adjustment valve of the electron microscope. The contact position between the sphere of the tungsten needle #2 and the side of the carbon nanocone needle tip #1 was maintained as it was, and a current of 0.6 A was applied to the two needle bodies for 10 min. After the heating was completed, the carbon nanocone functionalized needle tip was quickly removed while avoiding irradiation by the electron beam. After the electron microscope mode was returned to the high vacuum mode, nitrogen was introduced and the carbon nanocone needle tip was removed. The high-resolution morphology of the carbon nanocone needle tip was observed with a transmission electron microscope, and it was found that the carbon nanocone has a clean and complete graphite layer structure, as shown in Figure 5 (b).

[0043] EMBODIMENT 4 In this embodiment, the fabrication method of the carbon nanocone functionalized needle tip (as shown in FIG. 6(a)) is the same as that in embodiment 3.

[0044] The carbon nanocone functionalized needle tip was fixed to a ceramic needle tip clamping device with the needle tip facing upward, and placed in the heating area of ​​a tube vacuum furnace. The target temperature of the tube vacuum furnace was set to 500°C, the heating rate was 1°C / min, and the heat retention time was 60 min. Before the start of heating, carbon dioxide was introduced into the tube vacuum furnace and the flow rate of carbon dioxide was adjusted to 500 sccm. After the heating was completed, the needle tip was naturally cooled to room temperature, nitrogen was introduced, and the carbon nanocone needle tip was taken out and its structural characteristics were observed under a transmission electron microscope, as shown in Figure 6(b).

[0045] The above embodiments are merely for explaining the present application, and do not limit the present application. Although the present application has been described in detail with reference to the embodiments, those skilled in the art should understand that various combinations, modifications, or equivalent replacements for the technical solutions of the present application do not depart from the spirit and scope of the technical solutions of the present application, and should be included in the scope of the claims of the present application.

Claims

1. Step S201: Assembling a carbon nanocone on the tip of a needle base; S202 includes a step of heating the needle tip to a target temperature and introducing an active material to selectively react with contaminants on the surface of the needle tip to purify the carbon nanocone functionalized needle tip, the active material being carbon dioxide or water; In step S202, the method for manufacturing a carbon nanocone functionalized needle tip includes contacting a side surface of the needle body with the other metal body.

2. The manufacturing method according to claim 1, wherein in step S202, both the needle body and the separate metal body are fixed to a micro-nano manipulation arm, and their movements are controlled by the manipulation arm under microscope observation.

3. In step S202, when the side surface of the needle body is brought into contact with the other metal body, The method of claim 1, further comprising applying a continuous current between the needle body and the metal body to locally heat the needle tip to a high temperature and react with the active substance.

4. Assembling a carbon nanocone on the tip of a needle base The manufacturing method described in claim 1, characterized in that it includes using a micro-nano manipulation arm to control the tip of the needle tip base to enter inside the carbon nanocone, attaching the carbon nanocone to the tip of the needle tip base, contacting the needle tip base with another metal body, applying a voltage between the metal body and the needle tip base, passing a current through the needle tip base, heating the tip portion of the needle tip base and bonding it to the attached carbon nanocone.

5. The tip of the needle tip base of the carbon nanocone functionalized needle tip is decorated with carbon nanocones; The manufacturing method described in claim 1, characterized in that the carbon nanocone is a cone-shaped carbon nanomaterial having a layered graphite structure, the material of the needle tip base is one or more metals selected from tungsten, iron, cobalt, nickel, and titanium, the tail end of the carbon nanocone and the needle tip base form a covalent interface connection, the orientation of the tip of the carbon nanocone is consistent with the orientation of the central axis of the needle tip, the surface of the tip of the carbon nanocone is clean, and the structure of the graphite layer is complete.

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