Preparation method of three-dimensional carbon material with controllable structure

Abstract

The invention provides a preparation method of a three-dimensional carbon material with a controllable structure, and relates to the field of nano materials, and the preparation method comprises the following steps: coating a photosensitive photoresist on the surface of a cleaned substrate, and then performing exposure and development to form a specific pattern; putting the sample into a heating area of PECVD (Plasma Enhanced Chemical Vapor Deposition) equipment and heating the substrate to a preset temperature; introducing carrier gas into the reaction chamber, stopping introducing gas after annealing is completed, and waiting for the pressure in the reaction chamber to be natural and stable; introducing reaction gas into the reaction chamber, starting the plasma source, and setting output power; and after the preset growth time is reached, closing the plasma source and the hydrogen supply, and stopping the heating system at the same time. According to the method, the photoetching technology and PECVD are combined for growing the three-dimensional carbon material, the process is simple and efficient, complex etching and filling steps are not needed, additional pressing operation is not needed, the preparation process is greatly simplified, and the precisely patterned three-dimensional graphene structure can be obtained.

Description

Technical Field

[0001] The present invention relates to the field of nanomaterials, and particularly to a method for preparing a three-dimensional carbon material with a controllable structure. This method aims to achieve the precise preparation of patterned three-dimensional graphene through precise process control. Background Art

[0002] As a two-dimensional material composed of single-layer carbon atoms in sp 2 hybrid orbitals, graphene has excellent properties such as being thin, light, highly electrically conductive, highly thermally conductive, high mobility, high specific surface area, and high mechanical strength, and is a potential two-dimensional material. It plays an important role and has a wide range of application prospects in modern technology. It can be applied to multiple application fields such as foldable electronic products, microcircuits and electronic devices, photodetectors, sensors, solar absorbers, supercapacitors, etc. And three-dimensional vertical graphene is prepared by plasma-enhanced chemical vapor deposition (PECVD). It can not only directly and rapidly grow graphene on the substrate, but also form a unique orientation structure perpendicular to the substrate. It retains the intrinsic properties of two-dimensional graphene, has exposed edges and a large specific surface area, forms a transport channel, and can expand to more extensive application fields.

[0003] In optoelectronic devices, three-dimensional graphene has more prominent advantages. It has excellent flexibility and stability, can improve the optoelectronic response performance, provide broadband optical characteristics, and enhance the light absorption and carrier separation efficiency. However, the light extraction or absorption in traditional device architectures is limited, and the performance of optoelectronic devices needs to be continuously optimized towards high efficiency, small size, and low power consumption, thus triggering the pursuit of innovation in nanomaterial production and patterning technologies.

[0004] Currently, the preparation technologies for patterned graphene mainly include the following methods: (1) Mechanical scratching patterning: Using an electric displacement system built in a glove box, direct writing patterning is achieved by mechanically scratching the surface of two-dimensional materials with a tungsten metal tip. However, this method will cause surface damage and the accuracy is limited, making it difficult to achieve precise pattern design. (2) Direct growth and transfer method: Patterned graphene is directly grown on a specific substrate and then transferred to an insulating substrate. However, this method cannot precisely control the positioning of graphene on the substrate, and contamination and wrinkles may be introduced during the transfer process, affecting the device performance. (3) Template imprinting method: Graphene patterns are formed in specific areas through template imprinting technology. This method is simple to operate, but the preparation cost of the template is high, and it is difficult to prepare complex patterns, limiting its application in high-precision micro-nano optoelectronic devices.

[0005] Therefore, it is particularly urgent to develop a new method for preparing a three-dimensional carbon material with a controllable structure that is highly efficient, low-power, and small-sized. Summary of the Invention

[0006] The present invention aims to provide a method for preparing three-dimensional carbon materials with controllable structures. The method can achieve high-precision, low-cost, and small-size patterned preparation while maintaining the excellent performance of three-dimensional vertical graphene, providing a new material solution for the development of micro-nano optoelectronic devices.

[0007] To achieve the above object, the method comprises the following steps:

[0008] (1) Substrate treatment: Use acetone, ethanol, and deionized water to ultrasonically clean the substrate.

[0009] (2) Patterned photolithography: A photosensitive photoresist is coated on the surface of the cleaned substrate for subsequent graphene growth. The photoresist is then exposed to ultraviolet light and a mask and then developed with a developer to remove the photoresist in specific areas.

[0010] (3) PECVD pre-reaction: Place the sample obtained in step (2) into the heating zone of the PECVD equipment, and evacuate the reaction chamber to reduce the pressure to the required vacuum level to ensure stable plasma generation. Then, turn on the heating zone and heat the substrate to a preset temperature. The temperature should be kept uniform and stable during the heating process. When the substrate temperature reaches the preset value, keep the temperature constant.

[0011] (4) Introducing carrier gas for annealing: Introduce carrier gas into the reaction chamber and control the flow rate. After annealing is completed, close the carrier gas valve, stop ventilation, and wait for the pressure in the reaction chamber to stabilize naturally.

[0012] (5) Continue to introduce the reaction gas: After the above pressure is stable, introduce the reaction gas into the reaction chamber, start the plasma source, and set the appropriate output power. Active species such as ionized electrons, ions and free radicals are formed in the plasma and react chemically with the solid carbon source of the photoresist placed on the substrate. These active species react with the carbon atoms in the photoresist to promote the growth of graphene. The growth time of graphene is strictly controlled to achieve the desired thickness and structure.

[0013] (6) Turn off the plasma source and gas supply: After the predetermined growth time is reached, turn off the plasma source and the reaction gas supply. At the same time, stop the heating system. In a vacuum atmosphere, let the sample cool naturally to ambient temperature before taking it out.

[0014] Furthermore, in step (1), the substrate is cleaned for 15 minutes each time, and each solvent is used for cleaning three times. After cleaning, the substrate is dried with a nitrogen gun to ensure that the photoresist can be evenly coated on the substrate surface.

[0015] Further, in step (1), the substrate is a metal substrate or a non-metal substrate. Among them, the non-metal substrate is selected from at least one of a silicon substrate, a silicon oxide substrate, and SiO 2 / Si; the metal substrate is selected from at least one of a copper sheet and a nickel sheet.

[0016] Further, in step (2), the photosensitive photoresist is divided into two types, positive photoresist and negative photoresist, according to its chemical properties. Among them, the negative photoresist is SU-8, and the positive photoresist is SPR220.

[0017] Further, in step (2), the patterning lithography process is well-known to those skilled in the art and includes the following steps: uniformly coat a layer of photosensitive photoresist on the surface of the cleaned substrate for subsequent graphene growth; then perform soft baking on the substrate coated with the photoresist to remove the solvent in the photoresist and form a uniform film. The soft baking temperature for the negative photoresist SU-8 is 65~95°C, and the soft baking time is 1~120 min; while for the positive photoresist SPR, the soft baking temperature is 115°C, and the soft baking time is 90 s; next, use ultraviolet light with a wavelength of 365 nm to expose the photoresist through a pre-designed mask to form the required pattern. The exposure time and intensity need to be controlled during the exposure process. Among them, the exposure dose of the negative photoresist SU-8 is 60~600 mJ / cm 2 , and the exposure dose of the positive photoresist SPR is 160~380 mJ / cm 2 , to ensure the accurate transfer of the pattern; then perform post-baking to cure the photochemical reaction and enhance the stability of the pattern. The post-baking temperature for the negative photoresist SU-8 is 65~95°C, and the post-baking time is 3~45 min, while for the positive photoresist SPR, the post-baking temperature is 115°C, and the post-baking time is 30~120 s. Finally, immerse the exposed silicon wafer in the developer. The negative photoresist is developed until the film in all areas except the exposed area is completely dissolved, and the positive photoresist is developed until the film in all areas except the unexposed area is completely dissolved, and the development is detected under a microscope. Through these steps, the accuracy and repeatability of the patterning process are ensured, laying a foundation for the subsequent preparation of three-dimensional carbon materials.

[0018] Further, in step (3), the vacuum pressure of the reaction is 2×10 -3 ~ 8×10 -2 mbar.

[0019] Further, in step (3), the preset temperature of the reaction heating zone is 600~1200°C, and the holding time is 300 minutes. During the pre-reaction stage, the PECVD equipment is heated and set, and the temperature uniformity and stability should be maintained during the heating process. When the substrate temperature reaches the preset value, keep the temperature constant.

[0020] Further, in step (4), the carrier gas is selected from hydrogen, argon, nitrogen, or a mixed gas of hydrogen and argon. Annealing is used to pattern the photoresist into a carbon thin film at high temperature, repair the lattice defects in the carbon thin film, optimize the electrochemical properties of the carbon thin film, increase the carrier mobility, and reduce the resistivity.

[0021] Further, in step (4), in the mixed gas of hydrogen and argon, the volume ratio of hydrogen to argon is 1:(3 - 40), and the annealing time is 10 - 120 minutes.

[0022] Further, in step (5), the plasma power is 200 - 500 W, and the reaction time is 10 - 60 min. The change in plasma power will change the electron temperature and sheath potential, thus affecting the kinetic energy of ions and the reaction rate. At high power, the electron temperature and ion kinetic energy in the plasma increase, which may cause the graphene sheets to become thinner or even break; too low power may result in insufficient concentration of active particles, unable to effectively promote the decomposition of the carbon source and the nucleation growth of graphene, leading to a slow growth rate and a decrease in the quality of graphene. The length of the reaction time can significantly affect its morphology and properties. Too long a reaction time may lead to excessive growth of graphene, forming relatively thick sheets, affecting its conductivity and transparency, and may also increase the structural defects of graphene, thereby reducing its mechanical strength and electrical properties; too short a reaction time may result in insufficient growth of graphene, forming an incomplete sheet structure. In this case, the coverage and uniformity of graphene may be insufficient, resulting in poor material properties.

[0023] Further, in step (5), the reaction gas is hydrogen, and the gas flow rate is 2 - 50 sccm, preferably 10 sccm. Hydrogen decomposes into hydrogen radicals (H) in the plasma, and these radicals have a dual role of growth and etching during the growth of graphene. Hydrogen radicals can terminate the edge growth of graphene grains, thereby controlling the size and shape of the grains. By adjusting the flow rate of hydrogen and the plasma power, the growth rate and quality of graphene can be precisely controlled.

[0024] The present invention also provides a three-dimensional carbon material prepared by the above method.

[0025] The present invention also provides an application of the three-dimensional carbon material in micro-nano optoelectronic devices.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) Traditional CVD methods mostly rely on gaseous carbon sources, while the present invention uses a patterned photoresist as a solid carbon source without the need for additional gaseous carbon sources. The solid carbon source can improve the consistency and stability of graphene growth, reduce the uncertainty during the use of gaseous carbon sources, and enable more precise control of the structure and quality of graphene. Therefore, the present invention uses photolithography to fabricate the pattern of the solid carbon source, which can ensure the growth of three-dimensional graphene according to the photolithography pattern at the micro-nano scale.

[0028] (2) The present invention combines photolithography and PECVD for the growth of three-dimensional carbon materials. The process is simple and efficient, without the need for complex etching and filling steps, nor additional lamination operations. It greatly simplifies the preparation process, avoids complex transfer and etching processes, and can maintain the quality and integrity of graphene. Moreover, it is not limited to growing three-dimensional carbon materials on the surface of metal substrates and has more selectivity for substrates.

[0029] (3) The present invention can obtain a precisely patterned three-dimensional graphene structure, which has excellent chemical stability, good thermal conductivity, high electrical conductivity, excellent mechanical properties, high specific surface area, porous structure and other structural property characteristics. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0031] Figure 1 It is the macroscopic SEM image of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 1 of the present invention.

[0032] Figure 2 It is the microscopic SEM image of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 1 of the present invention.

[0033] Figure 3 It is the Raman spectrum of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 1 of the present invention.

[0034] Figure 4 It is the I-V characteristic diagram of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 1 of the present invention.

[0035] Figure 5 It is the microscopic SEM image of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 2 of the present invention.

[0036] Figure 6This is the Raman spectrum of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 2 of the present invention.

[0037] Figure 7 This is the I-V characteristic diagram of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 2 of the present invention.

[0038] Figure 8 This is the microscopic SEM image of the three-dimensional vertical graphene prepared in Comparative Example 1 of the present invention.

[0039] Figure 9 This is the microscopic SEM image of the sample obtained in Comparative Example 2 of the present invention. Detailed implementation manners

[0040] To make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following will be described in detail with reference to the accompanying drawings and specific embodiments.

[0041] Example 1

[0042] Use lithography technology to prepare three-dimensional carbon materials at the micro-nano scale. Use acetone (99.9%), ethanol (99.5%) and deionized water to ultrasonically clean the silicon wafer substrate three times, with each cleaning time being 15 minutes, to thoroughly remove surface impurities. After cleaning, dry it with a nitrogen gun to ensure that the photoresist can be evenly coated. Next, select the negative photoresist SU-8-2010, and optimize the patterning process by precisely adjusting the spin coating parameters, exposure conditions, baking conditions, and development conditions. Among them, the spin coating speed is 4000 rpm, the soft baking temperature and time are 95 °C, 2 - 3 min, the exposure uses ultraviolet light with a wavelength of 365 nm, and the exposure dose is 110 - 140 mJ / cm 2 , the post-baking temperature and time are 95 °C, 6 - 8 min, and the development time is 2 min, finally realizing the preparation of solid carbon source patterning with nanometer-level precision.

[0043] Subsequently, regulate the growth of three-dimensional graphene by PECVD. First, place the prepared solid carbon source substrate in the reaction chamber of a tube-type plasma enhanced chemical vapor deposition device, and ensure that it is located at the center of the heating area, and the distance between this position and the radio frequency power supply coil is 35 cm. Then start the vacuum pumping system to 2×10 -3 mbar ~ 8×10 -2mbar, then turn on the heating system and raise the temperature to 900 °C. After reaching the predetermined temperature, introduce argon into the tube at a flow rate of 10 sccm and perform high-temperature annealing for 30 minutes. After the annealing is completed, turn off the argon. After waiting for the pressure to stabilize, introduce hydrogen at a flow rate of 5 sccm and adjust the output power of the plasma source to increase from 200 W to 500 W. After 10 minutes, turn off the plasma source and hydrogen, and stop heating. Cool to room temperature under continuous vacuum pumping. Finally, patterned-growth three-dimensional graphene at the micro-nano composite scale is obtained, which can be used in micro-nano optoelectronic devices.

[0044] Among them, Figure 1 This is the macroscopic SEM image of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 1 of the present invention. This figure is exactly the same as the designed zigzag pattern, and the zigzag line structure is the three-dimensional graphene carbon material. Figure 2 This is the microscopic SEM image of the patterned micro-nano composite scale three-dimensional graphene prepared in Example 1 of the present invention. This figure clearly presents the microscopic morphology of the three-dimensional graphene carbon material at the zigzag line structure.

[0045] Figure 3 This is the Raman spectrum of the patterned micro-nano composite scale three-dimensional graphene obtained in this example. Among them, the G peak is located at about 1580 cm - ⁻¹, reflecting the in-plane vibration mode of graphene, while the D peak appears near 1350 cm - ⁻¹, indicating the defects or edges present in the sample, and the 2D peak appears around 2680 cm - ⁻¹, which is a two-phonon resonance peak. These characteristic peaks together depict the microscopic structure and electronic properties of graphene. Figure 4 This is the I-V characteristic diagram of the patterned micro-nano composite scale three-dimensional graphene obtained in this example. Through precise measurement, on an area of 2.85×10 5 μm 2 ², the resistance value of this structure is 195 Ω. This result shows that the prepared three-dimensional graphene has a low resistivity, which is of great significance for its application in micro-nano electronic devices.

[0046] Example 2

[0047] Fabricating three-dimensional carbon materials at the micro-nano scale using lithography technology. Quartz substrates were ultrasonically cleaned three times with acetone (99.9%), ethanol (99.5%) and deionized water respectively, with each cleaning time being 15 minutes, to thoroughly remove surface impurities. After cleaning, they were dried with a nitrogen gun to ensure that the photoresist could be uniformly coated. Next, positive photoresist SPR220-4.5 was selected, and by precisely adjusting the spin-coating parameters, exposure conditions, baking conditions, and development conditions, the patterning process was optimized, and finally, the preparation of a solid carbon source pattern with nanoscale precision was achieved. Among them, the spin-coating speed was 4000 rpm, the soft baking temperature and time were 115 °C, 90 s, the exposure used ultraviolet light with a wavelength of 365 nm, and the exposure dose was 330 - 360 mJ / cm 2 , the post-baking temperature and time were 115 °C, 60 s, and the development time was 140 s.

[0048] Subsequently, the growth of three-dimensional graphene was regulated by PECVD. First, the prepared solid carbon source substrate was placed in the reaction chamber of a tube-type plasma-enhanced chemical vapor deposition equipment, and it was ensured that it was located at the center of the heating area, and the distance between this position and the radio frequency power supply coil was 35 cm. Then, the vacuum pumping system was started to 2×10 -3 mbar ~ 8×10 -2 mbar, and then the heating system was turned on to raise the temperature to 900 °C. After reaching the predetermined temperature, argon was introduced into the tube with a flow rate of 10 sccm for high-temperature annealing treatment for 30 minutes. After the annealing ended, the argon was turned off. After waiting for the pressure to stabilize, hydrogen was introduced with a flow rate of 5 sccm, and the output power of the plasma source was adjusted to rise from 200 W for starting the glow discharge to 500 W. After 10 minutes, the plasma source and hydrogen were turned off, and the heating was stopped. It was cooled to room temperature under continuous vacuum pumping, and finally, the micro-nano composite-scale three-dimensional graphene with patterned growth was obtained, which can be used in micro-nano optoelectronic devices.

[0049] Among them, Figure 5 is the microscopic SEM image of the patterned micro-nano composite-scale three-dimensional graphene prepared in Example 2 of the present invention. The microscopic structure of graphene is clearly presented in the figure. This structure not only retains the excellent electrical and mechanical properties of two-dimensional graphene, but also significantly improves the specific surface area and electrochemical properties of the material through its vertical orientation and porous characteristics. Figure 6 is the Raman spectrum of the patterned micro-nano composite-scale three-dimensional graphene obtained in this example. Among them, the G peak is located at about 1580 cm - ⁻¹, reflecting the in-plane vibration mode of graphene, while the D peak appears at around 1350 cm - ⁻¹, indicating the defects or edges present in the sample, and the 2D peak is at 2680 cm -¹Appear on both sides, which are double phonon resonance peaks. These characteristic peaks together depict the microscopic structure and electronic properties of graphene. Figure 7 This is the I-V characteristic diagram of the patterned micro-nano composite scale three-dimensional graphene obtained in this embodiment. Through precise measurement, on an area of 1.3×10 5 μm 2 the resistance value of this structure is 914 Ω. This result indicates that the prepared three-dimensional graphene has a low resistivity, which is of great significance for its application in micro-nano electronic devices.

[0050] Comparative Example 1

[0051] Directly grow three-dimensional vertical graphene on the substrate by PECVD:

[0052] Put the cleaned silicon substrate in the center of the heating zone of the plasma enhanced chemical vapor deposition equipment. The distance between the center of the heating zone and the RF power supply coil is 35 cm. Then close the exhaust valve and evacuate. Turn on the heating of the heating zone to heat the substrate. After reaching the set temperature of 900 °C, keep the temperature constant. Subsequently, introduce hydrogen into the tube at a flow rate of 20 sccm to reduce the oxides on the substrate surface. After 3 minutes, turn on the plasma source, set the output power to 200 W, and ionize hydrogen to further reduce the oxides on the substrate surface. After 2 minutes, turn off the hydrogen and the plasma source; 2 minutes later, introduce hydrogen and hydrocarbon again, the hydrogen flow rate is 2 sccm, the acetylene flow rate is 6 sccm, set the plasma source output power to 500 W, and carry out growth. After 1 h, turn off the heating and the plasma source, and naturally cool to the ambient temperature under vacuum to obtain three-dimensional vertical graphene.

[0053] Among them, Figure 8 This is the microscopic morphology diagram of the three-dimensional vertical graphene prepared in Comparative Example 1, indicating that a vertically oriented three-dimensional graphene structure grows on the substrate surface. If patterning is to be achieved, a series of relatively complex processing steps are required subsequently to form the required pattern. It shows that the growth of graphene on the substrate surface can be achieved by the method of Comparative Example 1, but a refined pattern cannot be formed.

[0054] Comparative Example 2

[0055] Anneal the sample after lithography using PECVD: Ultrasonically clean the silicon wafer substrate three times with acetone (99.9%), ethanol (99.5%), and deionized water respectively, with each cleaning time being 15 minutes to thoroughly remove surface impurities. After cleaning, dry it with a nitrogen gun to ensure that the photoresist can be evenly coated. Next, select the negative photoresist SU-8-2010, and optimize the patterning process by precisely adjusting the spin-coating parameters, exposure conditions, baking conditions, and development conditions. Among them, the spin-coating speed is 4000 rpm, the soft baking temperature and time are 95°C, 2 - 3 min, the exposure uses ultraviolet light with a wavelength of 365 nm, and the exposure dose is 110 - 140 mJ / cm 2 , the post-baking temperature and time are 95°C, 6 - 8 min, the development time is 2 min, and finally, the preparation of a solid carbon source pattern with nanoscale precision is achieved.

[0056] Subsequently, anneal the sample by PECVD. First, place the prepared solid carbon source substrate into the reaction chamber of a tube-type plasma-enhanced chemical vapor deposition equipment, and ensure that it is located at the center of the heating area, and the distance between this position and the radio frequency power supply coil is 35 cm. Then start the vacuum pumping system to 2×10 -3 mbar ~ 8×10 -2 mbar, and then turn on the heating system to raise the temperature to 900°C. After reaching the predetermined temperature, introduce argon into the tube with a flow rate of 10 sccm for high-temperature annealing treatment for 30 minutes. After the annealing is completed, turn off the argon and stop heating, and cool to room temperature under the condition of continuous vacuum pumping.

[0057] Among them, Figure 9 is the microscopic morphology diagram of the sample obtained in Comparative Example 2. It shows that the effect of high-temperature annealing is not good, there is too little graphene on the substrate surface, and the ideal graphene effect is not generated.

[0058] The above-mentioned examples and comparative examples illustrate that by using the method of the present invention, first, the substrate is patterned by lithography technology, and then three-dimensional graphene is grown on the patterned substrate, achieving precise control of the graphene structure. This process is simple to operate, greatly simplifies the industrial production process, and provides an efficient solution for manufacturing high-quality graphene of any shape. Combining the advantages of patterning technology with the unique physical and chemical properties of graphene, the present invention lays a solid foundation for the development of high-performance micro-nano optoelectronic devices.

[0059] The above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, and all should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for preparing a three-dimensional carbon material with a controllable structure, characterized in that: The method comprises the following steps: (1) Substrate treatment: ultrasonically clean the substrate using acetone, ethanol, and deionized water in sequence; (2) Patterned photolithography: A photosensitive photoresist is coated on the cleaned substrate surface, then exposed to ultraviolet light and a mask, and then developed with a developer to remove the photoresist in specific areas; (3) PECVD pre-reaction: the sample obtained in step (2) is placed in the heating zone of the PECVD equipment, and the pressure in the reaction chamber is reduced to the required vacuum degree by evacuating the chamber, and then the heating zone is turned on to heat the substrate to a preset temperature; (4) Introducing carrier gas for annealing: Introduce carrier gas into the reaction chamber. After annealing is completed, close the carrier gas valve, stop ventilation, and wait for the pressure in the reaction chamber to stabilize naturally; (5) Continue to introduce the reaction gas: After the pressure is stabilized, introduce the reaction gas into the reaction chamber, start the plasma source, and set the output power; (6) Turn off the plasma source and gas supply: After the predetermined growth time is reached, turn off the plasma source and the reaction gas supply, and stop the heating system. In a vacuum atmosphere, let the sample cool naturally to ambient temperature before taking it out.

2. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (1), the substrate is a metal substrate or a non-metal substrate, wherein the non-metal substrate is selected from at least one of a silicon substrate, a silicon oxide substrate, and SiO2 / Si; and the metal substrate is selected from at least one of a copper sheet and a nickel sheet.

3. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (2), the photosensitive photoresist is a positive photoresist or a negative photoresist, wherein the negative photoresist is SU-8 and the positive photoresist is SPR220.

4. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (3), the vacuum pressure of the reaction is 2×10 -3 ~ 8×10 -2 mbar.

5. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (3), the preset temperature of the reaction heating zone is 600-1200° C., and the insulation time is 300 minutes.

6. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (4), the carrier gas is selected from hydrogen, argon, nitrogen or a mixture of hydrogen and argon, the volume ratio of hydrogen to argon in the mixture of hydrogen and argon is 1:(3~40), and the annealing time is 10~120 minutes.

7. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (5), the plasma power is 200-500 W and the reaction time is 10-60 min.

8. The method for preparing a three-dimensional carbon material with a controllable structure according to claim 1, characterized in that: In step (5), the reaction gas is hydrogen, and the gas flow rate is 2 to 50 sccm, preferably 10 sccm.

9. The three-dimensional carbon material prepared by the method according to any one of claims 1 to 8.

10. Use of the three-dimensional carbon material according to claim 9 in micro-nano optoelectronic devices.

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