WO2020168819A1 - 一种高效消除化学气相沉积法石墨烯褶皱的方法 - Google Patents

一种高效消除化学气相沉积法石墨烯褶皱的方法 Download PDF

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WO2020168819A1
WO2020168819A1 PCT/CN2019/127803 CN2019127803W WO2020168819A1 WO 2020168819 A1 WO2020168819 A1 WO 2020168819A1 CN 2019127803 W CN2019127803 W CN 2019127803W WO 2020168819 A1 WO2020168819 A1 WO 2020168819A1
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graphene
plasma
reaction
wrinkles
vapor deposition
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高力波
袁国文
徐洁
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Nanjing University
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Nanjing University
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Priority to GB2105298.0A priority patent/GB2592513B/en
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Definitions

  • the invention relates to the field of graphene growth, in particular to a new method for efficiently eliminating the wrinkles of chemical vapor deposition graphene.
  • CVD graphene Although the CVD method produces high-quality graphene, there are always some shortcomings compared with the performance of the most intrinsic graphene. The fundamental reason is that CVD graphene always has defects. On the one hand, it comes from grain boundaries and wrinkles in the growth process, and on the other hand, it is the folding, breakage and tearing introduced by the transfer process. Although researchers have grown centimeter-level graphene single crystals to eliminate the influence of grain boundaries and optimize the transfer process to eliminate the impact of folding damage, there is no essential improvement in the performance of CVD graphene, an important reason It is because of the ubiquity of wrinkles.
  • the generation of wrinkles comes from the high temperature growth environment of CVD.
  • the temperature difference and the thermal expansion rate difference between the graphene and the substrate cause the graphene to produce inevitable wrinkles.
  • the wrinkled area is more likely to introduce some vacancy defects, reducing the oxidation resistance of graphene, resulting in uneven mass distribution of the graphene film. Therefore, improving the existing CVD method and exploring the means to control graphene wrinkles, fundamentally eliminate wrinkles, and prepare high-quality, large-area ultra-flat graphene films are the key to realizing the real application of graphene to high-quality devices. .
  • the purpose of the present invention is to provide a new method for efficiently eliminating graphene wrinkles and CVD to prepare graphene, which is mainly used for the preparation of high-quality wrinkle-free graphene, or to reduce and completely eliminate graphene wrinkles.
  • the present invention reduces and eliminates the wrinkles in the CVD graphene sample through precise experimental control so that the intrinsic properties are retained.
  • the size of the crease-free graphene prepared by the invention reaches the wafer level, so it can be used as an ideal method for device assembly and basic research.
  • the present invention provides a variety of substrates that are simultaneously injected with protons during growth to directly grow ultra-flat graphene without wrinkles. It also includes a method for post-treatment of proton-injected graphene with wrinkles grown by traditional methods to reduce and eliminate wrinkles .
  • the technical solution of the present invention is: a method for efficiently eliminating graphene wrinkles by chemical vapor deposition, which is characterized by: using controllable proton injection in a high-temperature environment, and accurately controlling the temperature environment and the hydrogen plasma power for generating protons.
  • controllable proton injection in a high-temperature environment, and accurately controlling the temperature environment and the hydrogen plasma power for generating protons.
  • the plasma-assisted chemical vapor deposition system includes a plasma generator, a vacuum system, a heating system, etc.; the power of the plasma generator can be adjusted from 5 to 1000W, and the vacuum system can be adjusted to pressure from 10 -5 to 10 5 Pa. Control heating temperature range 25 ⁇ 1000°C;
  • the plasma-assisted chemical vapor deposition technology used adjusts the reaction atmosphere and gas flow, reaction pressure, heating temperature, heating time, plasma power and reaction time;
  • the reaction gas can be methane, nitrogen, argon, helium, hydrogen, etc.
  • the gas flow rate is 50 ⁇ 2000sccm;
  • the reaction pressure is 1 ⁇ 20Pa;
  • the heating temperature is 500 ⁇ 1000°C, the heating time is 5min ⁇ 2h;
  • the plasma power is 5 ⁇ 200W, and the plasma reaction time is 60s ⁇ 3600s.
  • Plasma-assisted chemical vapor deposition system Heating for a certain period of time and supplemented by a specific hydrogen pressure, while adjusting the appropriate coupling matching power and reaction time, plasma reaction, can reduce and eliminate graphene wrinkles; the used plasma
  • the auxiliary chemical vapor deposition technology adjusts the reaction temperature, pressure, reaction gas flow, heating time, plasma intensity and reaction time.
  • the reaction temperature is 100 ⁇ 1000°C; the reaction pressure is 1 ⁇ 100Pa; the reaction gas can be hydrogen; gas flow It is 5 ⁇ 2000sccm; heating time is 60 ⁇ 3600s; plasma reaction time is 60 ⁇ 1800s.
  • the reaction substrate in the present invention is various metals such as copper, nickel, platinum, iridium, ruthenium, tungsten, gold, silver and their alloys, and various non-metallic substrates such as silicon oxide, aluminum oxide and silicon carbide.
  • the plasma-assisted chemical vapor deposition system in the present invention includes a plasma generator, a vacuum system, a heating system and the like.
  • the plasma generator is an inductively coupled radio frequency plasma with an adjustable power range of 5 to 1000W, an adjustable pressure of 10 -5 to 10 5 Pa in the vacuum system, and a controllable heating temperature range of 25 to 1000°C.
  • the reaction substrate is a variety of metals such as copper, nickel, platinum, iridium, ruthenium, tungsten, gold, and silver, and a variety of non-metallic substrates such as silicon oxide, aluminum oxide, and silicon carbide.
  • the size of the sample is not limited, it only depends on the design of the reaction system.
  • the plasma generator is an inductively coupled plasma generator, and the power adjustable range is 5W ⁇ 1000W.
  • the preferred power is 10W-20W, and in the process of plasma post-processing the wrinkled graphene, the preferred power is 20W-100W.
  • the plasma-assisted chemical vapor deposition system is an inductively coupled plasma generator, and the power adjustable range is 5W ⁇ 1000W. In the process of directly preparing unfolded graphene, the preferred power is 10W-20W, and in the process of plasma post-processing the wrinkled graphene, the preferred power is 20W-100W.
  • the plasma-assisted chemical vapor deposition technology used adjusts the reaction temperature, pressure, reaction gas flow, heating time, plasma intensity and reaction time.
  • the reaction temperature is 500-1000°C; the pressure is 1-20 Pa; the reaction gas can be Carbon source gas and carrier gas, including methane, nitrogen, argon, helium, hydrogen, etc.; gas flow rate is 50-1000sccm; heating time is 5min-1h; plasma power is 5-200W, and reaction time is 60s-3600s.
  • the wrinkled graphene is prepared by chemical vapor deposition method, adjusting reaction temperature, pressure, and carrier gas flow rate to grow graphene film.
  • the reaction temperature is 600 ⁇ 1400°C; the pressure is 10 -2 ⁇ 10 5 Pa; the carbon source gas can be: methane, ethylene, acetylene, various gaseous carbon-containing organic substances (liquid or solid), and the gas flow can be 10 -5 ⁇ 100sccm ;
  • the carrier gas can be hydrogen, nitrogen, helium, argon, etc.; the gas flow is generally 5 to 5000 sccm.
  • the reaction time is 5 ⁇ 3600s.
  • the heating time is 60-3600s, the heating temperature is 100-1000°C; the plasma power is 10-500W, the plasma reaction time is 1-30min, and the reaction pressure is 1-100Pa.
  • the height of wrinkles can be effectively controlled to reduce or eliminate, and for single-layer graphene, it can be less than or equal to 3nm.
  • the size of the sample in the present invention can be any size and only depends on the design of the reaction system.
  • the invention adopts the combination of vacuum heating and plasma assist.
  • CVD method to grow on copper, nickel, platinum, iridium, ruthenium, gold, silver and other metals, silicon oxide, aluminum oxide, silicon carbide and other non-metals as substrates.
  • the wrinkled graphene that comes out, by adjusting the heating temperature and hydrogen plasma power and time, using the principle of proton selective permeation, effectively reducing and eliminating wrinkles, so as to achieve a flatter graphene; on the other hand, through Adding hydrogen plasma while CVD growth can directly produce wrinkle-free graphene.
  • This kind of regulation can realize the preparation of more flat graphene, and provides support for the preparation method for the optimization of high-performance graphene single crystals and thin films.
  • the invention can effectively reduce and eliminate wrinkles in graphene prepared by chemical vapor deposition by accurately controlling environmental temperature and pressure, and simultaneously changing the power and action time of hydrogen plasma for generating protons through proton injection in a high-temperature environment.
  • This method is suitable for graphene with wrinkles grown on various substrates, such as copper, platinum, nickel, iridium, ruthenium, tungsten, gold, silver and other metals and their alloys, silicon oxide, silicon carbide, nitride Various non-metals such as silicon.
  • the present invention utilizes the proton permeability of graphene and the impermeability of atomic hydrogen to generate a certain concentration of protons through the controllable hydrogen plasma, and the protons can recombine into hydrogen atoms and hydrogen molecules after penetrating the graphene.
  • Changing the coupling force between the graphene and the growth substrate can effectively control and eliminate the wrinkles of graphene.
  • the wrinkle-free graphene directly grown or post-processed, including graphene single crystal grains and films, can be of any size. Wrinkle-free graphene exhibits higher electrical properties. This kind of direct growth and post-processing wrinkle-free graphene Graphene provides technical support for sample preparation for high-quality graphene in the future flexible electronic devices, micro-nano optoelectronic devices and other fields.
  • the present invention uses plasma to directly grow graphene without wrinkles, which greatly improves the quality of graphene.
  • the graphene surface is ultra-flat, with few defects and high quality.
  • the present invention can effectively adjust the wrinkle height and distribution of graphene by adjusting heating temperature, heating time, plasma power, and plasma reaction time.
  • the present invention does not use any harmful substances, is simple and efficient, and wrinkle-free graphene can be produced in a very short time.
  • the present invention is a universal method that can be applied to various metals such as copper, nickel, platinum, iridium, ruthenium, tungsten, gold, silver and their alloys, and various non-metallic substrates such as silicon oxide, aluminum oxide, and silicon carbide. Used on.
  • the present invention can effectively reduce and eliminate wrinkles in graphene by chemical vapor deposition through high-temperature heating and proton injection under hydrogen plasma, and by accurately controlling heating temperature and plasma power.
  • the ultra-flat, wrinkle-free high-quality graphene film be directly grown on a variety of substrates, but also can reduce and eliminate the graphene wrinkles grown by the ordinary CVD method through post-processing.
  • the ultra-flat, wrinkle-free graphene film can be of any size, depending only on the design of the growth system.
  • Such controllable acquisition of wrinkle-free graphene can improve the performance of graphene grown by CVD method, and lays a preparation technology support for the realization of future applications in the fields of flexible electronic devices, high-performance electronics, and optoelectronic devices.
  • the method of the present invention is suitable for graphene with wrinkles grown on various substrates, such as copper, platinum, nickel, iridium, ruthenium, tungsten, gold, silver and other metals and their alloys, silicon oxide, silicon carbide, nitrogen Various non-metals such as silicon dioxide.
  • the present invention utilizes the proton permeability of graphene and the impermeability of atomic hydrogen to generate a certain concentration of protons through the controllable hydrogen plasma, and the protons can recombine into hydrogen atoms and hydrogen molecules after penetrating the graphene. Changing the coupling force between the graphene and the growth substrate can effectively control and eliminate the wrinkles of graphene.
  • the invention involves injecting protons on a variety of substrates while growing to directly grow ultra-flat graphene without wrinkles, and also includes post-injection treatment of protons with wrinkled graphene grown in a traditional way to reduce and eliminate wrinkles.
  • the wrinkle-free graphene directly grown or post-processed including graphene single crystal grains and films, can be of any size. Wrinkle-free graphene exhibits higher electrical properties. This kind of direct growth and post-processing wrinkle-free graphene Graphene provides technical support for sample preparation for high-quality graphene in the future flexible electronic devices, micro-nano optoelectronic devices and other fields.
  • Figure 1 Schematic diagram of reducing and removing graphene wrinkles on a copper substrate.
  • Unwrinkled graphene grown on a copper substrate (a) is a picture of a 20 cm unwrinkled graphene film; (b) the corresponding atomic force microscope picture; (c) is (b) the position marked on the black solid line The height map of; (d) is the Raman microscopic spectrum of unwrinkled graphene.
  • Figure 3 Unwrinkled graphene film transferred to the surface of a silicon wafer with an oxide layer: (a) optical photo; (b) atomic force microscope photo; (c) height map from the position marked by the black solid line in (b).
  • Figure 4 Atomic force microscope image measured before processing of wrinkled graphite.
  • Figure 5 Atomic force microscope image (without wrinkles) measured at the same position by post-processing the wrinkled graphene.
  • This method uses high-temperature heating and hydrogen plasma injection, through precise control of heating temperature and adjustment of plasma power, etc., so as to apply various metals such as copper and nickel and their alloys, silicon oxide, silicon carbide and other metal and non-metal substrates.
  • various metals such as copper and nickel and their alloys, silicon oxide, silicon carbide and other metal and non-metal substrates.
  • An ultra-flat graphene film with no wrinkles is grown on it.
  • the specific implementation example is as follows:
  • Plasma-assisted growth of graphene without wrinkles on the copper substrate specifically: a smooth copper film (plated on sapphire), placed in a tube furnace and heated to 1000°C and maintained for 40 minutes to obtain relatively smooth copper surface.
  • a smooth copper film plated on sapphire
  • the pressure of the reaction chamber is stabilized to 10Pa through a pressure regulating valve and heated to 500 ⁇ 800°C , And keep for 1 to 10 minutes.
  • Start the inductively coupled plasma generator adjust the power to 10-50W, and control the grain size and growth rate of the graphene film by changing the plasma power and time.
  • a single layer and no wrinkles can be obtained by growing for 2 to 5 minutes.
  • Graphene film After the growth is completed, the temperature is naturally cooled, and the gas is turned off when the temperature drops to near room temperature.
  • Plasma-assisted growth of graphene without wrinkles on the copper substrate specifically: a smooth copper film (plated on sapphire), placed in a tube furnace and heated to 1000°C and maintained for 40 minutes to obtain relatively smooth copper surface.
  • a smooth copper film plated on sapphire
  • the total gas flow rate can be 50-1000 sccm
  • the pressure of the reaction chamber is stabilized by a pressure regulating valve It is 10Pa, heated to 500 ⁇ 800°C, and kept for 30m minutes (in this embodiment, the retention time can be between 5min ⁇ 2h).
  • the inductively coupled plasma generator adjust the power to 10-50W, and control the grain size and growth rate of the graphene film by changing the plasma power and time.
  • a single layer and no wrinkles can be obtained by growing for 2 to 5 minutes.
  • Graphene film (in this embodiment, the growth time can be adjusted between 60 s and 3600 s to obtain pleated graphene grains and a single layer of pleated graphene film).
  • a non-wrinkle graphene is grown on a nickel substrate with plasma assistance.
  • the substrate uses nickel, platinum, gold, silver, rhodium, iridium, ruthenium and other metal and alloy films, taking nickel as an example
  • a smooth nickel film (plated on sapphire) is placed in a tube furnace and heated to 1000°C and maintained for 40 minutes to obtain a relatively smooth nickel surface.
  • the nickel substrate into the plasma-assisted chemical vapor deposition system, add hydrogen and methane, the ratio is 40:1 (total gas flow is 200sccm)
  • the pressure of the reaction chamber is stabilized to 10Pa through the pressure regulating valve, and heated to 500 ⁇ 800°C , And keep for 1 to 10 minutes.
  • the inductively coupled plasma generator adjust the power to 10-50W, and control the grain size and growth rate of the graphene film by changing the plasma power and time.
  • a single layer and no wrinkles can be obtained by growing for 2 to 5 minutes.
  • Graphene film After the growth is completed, the temperature is naturally cooled, and the gas is turned off when the temperature drops to near room temperature.
  • the substrate uses non-metallic substrates such as alumina, silicon oxide, silicon carbide, magnesium oxide, silicon, and hexagonal boron nitride.
  • Alumina example specifically: put the alumina substrate into the plasma-assisted chemical vapor deposition system, and pass in hydrogen and methane at a ratio of 10:1 (total gas flow rate is 200sccm), and stabilize the pressure of the reaction chamber through a pressure regulating valve It is 10Pa, heated to 800 ⁇ 1000°C, and kept for 1 ⁇ 10 minutes.
  • the inductively coupled plasma generator adjust the power to 50-200W, and control the grain size and growth rate of the graphene film by changing the plasma power and time.
  • a single layer, without wrinkles can be obtained by growing for 5-10 minutes Graphene film. After the growth is completed, the temperature is naturally cooled, and the gas is turned off when the temperature drops to near room temperature.
  • the substrate uses non-metallic substrates such as alumina, silicon oxide, silicon carbide, magnesium oxide, silicon, and hexagonal boron nitride.
  • Alumina example specifically: the alumina substrate is placed in a plasma-assisted chemical vapor deposition system, and hydrogen and methane are fed in at a ratio of 10:1 (in this embodiment, the total gas flow can be adjusted between 50 and 1000 sccm ), the pressure of the reaction chamber is stabilized to 10 Pa (in this embodiment, the pressure is 1-20 Pa), heated to 800-1000° C., and kept for 30 minutes (in this embodiment, the heat preservation time is adjusted to 5 min-2h).
  • the inductively coupled plasma generator adjust the power to 50-200W, and control the grain size and growth rate of the graphene film by changing the plasma power and time.
  • a single layer, without wrinkles can be obtained by growing for 5-10 minutes Graphene film. After the growth is completed, the temperature will drop naturally, and the gas will be turned off when the temperature drops to near room temperature
  • the wrinkles of graphene grown on the copper substrate are reduced and eliminated.
  • a wrinkled graphene film is grown on the copper substrate.
  • the wrinkled graphene Atmospheric growth using methane as the carbon source: Put the copper base into a tube furnace, add argon and hydrogen, the ratio is 10:1, the total gas flow is 500sccm, and then heat to 1000°C and keep for 40min annealing, then Inject 5-50 sccm of 1% diluted methane, grow at atmospheric pressure for 600-3600s, and then naturally cool down to obtain wrinkled graphene.
  • the pleated graphene is placed in a plasma-assisted chemical vapor deposition system, and hydrogen is introduced.
  • the pressure in the reaction chamber is stabilized at 10 Pa through a pressure regulating valve, and the reaction chamber is heated to 500-800° C. and maintained for 1-10 minutes.
  • Start the inductively coupled plasma generator adjust the power to 10-50W, and generally treat it for 1 to 5 minutes to effectively reduce and remove the wrinkles in the graphene film. After the treatment is completed, the temperature will drop naturally, and the gas will be turned off when the temperature drops to near room temperature.
  • the wrinkles of graphene grown on the copper substrate are reduced and eliminated.
  • the carbon source is Ethylene, acetylene, various gaseous carbon-containing organic substances (liquid or solid), the reaction pressure is between 10 -2 ⁇ 10 5 Pa, the carrier gas is hydrogen, helium, argon, etc.
  • the reaction pressure is 10 -1 pa
  • the total gas flow is 10 sccm
  • the reaction temperature is 800 °C
  • the growth time is 600 s.
  • a wrinkled graphene film is obtained on a copper substrate.
  • the pleated graphene is placed in a plasma-assisted chemical vapor deposition system, and hydrogen is introduced.
  • the pressure in the reaction chamber is stabilized at 10 Pa through a pressure regulating valve, and the reaction chamber is heated to 500-800° C. and maintained for 1-10 minutes.
  • Start the inductively coupled plasma generator adjust the power to 10-50W, and generally treat it for 1 to 5 minutes to effectively reduce and remove the wrinkles in the graphene film. After the treatment is completed, the temperature will drop naturally, and the gas will be turned off when the temperature drops to near room temperature.
  • the substrate uses nickel, platinum, gold, silver, rhodium, iridium, ruthenium and other metals and alloys Thin film, taking nickel as an example), specifically: First, place the wrinkled graphene film that has been grown on the nickel substrate in a plasma-assisted chemical vapor deposition system, and then pass in hydrogen gas to stabilize the pressure in the reaction chamber through a pressure regulating valve It is 10Pa, heated to 500 ⁇ 800°C, and kept for 1 ⁇ 10 minutes.
  • the inductively coupled plasma generator adjust the power to 10-50W, and generally treat it for 1 to 5 minutes to effectively reduce and remove the wrinkles in the graphene film. After the treatment is completed, the temperature will drop naturally, and the gas will be turned off when the temperature drops to near room temperature.
  • the heating time is 60-3600s, the heating temperature is 100-1000°C; the plasma power is 10-500W, the plasma reaction time is 1-30min, and the reaction pressure is 1-100Pa.
  • the specific difference from Embodiment 6 lies in the fact that high-temperature heating and plasma are used to reduce and eliminate the wrinkles of graphene grown on the alumina substrate.
  • the substrate uses alumina, silicon oxide, and carbide
  • Non-metallic substrates such as silicon, magnesia, silicon, hexagonal boron nitride, take alumina as an example
  • the graphene film with wrinkles that has been grown on the alumina substrate is placed in plasma-assisted chemical vapor deposition
  • hydrogen gas is introduced, the pressure of the reaction chamber is stabilized to 10 Pa through the pressure regulating valve, and the reaction chamber is heated to 800-1000°C and maintained for 1-10 minutes.
  • start the inductively coupled plasma generator adjust the power to 50-200W, and generally treat it for 5-10 minutes to effectively reduce and remove the wrinkles in the graphene film.
  • the temperature will drop naturally, and the gas will be turned off when the temperature drops to near room temperature.
  • the substrate uses alumina, silicon oxide, silicon carbide, magnesium oxide, silicon, hexagonal nitride
  • Non-metallic substrates such as boron, taking aluminum oxide as an example
  • first place the graphene film with wrinkles that has been grown on the aluminum oxide substrate in a plasma-assisted chemical vapor deposition system pass hydrogen, and adjust the pressure
  • the valve stabilizes the pressure of the reaction chamber at 10 Pa, heats it to 300°C (the lower heating temperature range in this embodiment is 100-500°C), and keeps it for 1-10 minutes.
  • the inductively coupled plasma generator start the inductively coupled plasma generator, adjust the power to 300W (in this embodiment, increase the reaction power, the range is between 200-500W), and treat for 20 minutes (in this embodiment, extend the treatment time) to effectively reduce and remove graphite Wrinkles in the olefin film.
  • the temperature will drop naturally, and the gas will be turned off when the temperature drops to near room temperature.
  • FIG. 1 a schematic diagram of reducing and removing graphene wrinkles on a copper substrate.
  • the wrinkle-free graphene film transferred to the surface of the silicon wafer with an oxide layer (a) optical photo; (b) atomic force microscope photo; (c) from the position marked by the black solid line in (b) Height map.

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Abstract

一种高效消除化学气相沉积法石墨烯褶皱的方法，利用在高温环境下的可控质子注入，通过精确控制温度环境和生成质子的氢气等离子体功率和时间，在铜、镍等各种金属及其合金，氧化硅、碳化硅等各种非金属基体上，直接生长出无褶皱的超平整石墨烯薄膜，或者消除带有褶皱的石墨烯上的褶皱；所述等离子体辅助化学气相沉积系统包括等离子体发生器，真空系统，加热系统；其中等离子体发生器功率5～1000W，真空系统10-5～105Pa，系统可控加热温度范围25～1000℃；多种衬底上在生长同时注入质子，直接生长出超平整的无褶皱石墨烯，也包括通过传统方式生长的带有褶皱石墨烯的质子注入后处理，减小和消除褶皱。

Description

一种高效消除化学气相沉积法石墨烯褶皱的方法 技术领域:
本发明涉及石墨烯生长领域，具体为涉及一种高效消除化学气相沉积石墨烯褶皱的新方法。
背景技术:
2004年，英国的曼彻斯特大学Andre Geim研究组首次采用胶带剥离法(或微机械剥离法)获得稳定存在的石墨烯。石墨烯独特的二维晶体结构，使其具有优异的电学、热学和力学性能，被认为将在透明导电薄膜，晶体管，功能复合材料、储能、催化等领域有着广阔的应用。因此找到合适的方法制备出大面积高质量的石墨烯薄膜对实现石墨烯应用的工业化十分重要。
目前，多种制备石墨烯的方法陆续被开发出来，包括机械剥离法，化学剥离法、外延生长法和化学气相沉积(CVD)法等。综合对比现有的制备方法，CVD法由于制备工艺简单，且质量高，产量较大，得到广泛的关注，是目前可控制备高质量石墨烯的重要方式，也是实现石墨烯工业化的重要手段。目前通过CVD法制备的石墨烯甚至超过了30英寸，为实现工业化应用取得了长足的进步。CVD法基本原理是在高温下反应衬底对碳源进行催化脱氢，从而在衬底上生长出多层或者单层的石墨烯。
尽管CVD法制备出高质量的石墨烯，但和最本征石墨烯的性能相比，总是存在着一些不足。其根本原因在于CVD石墨烯总是存在着缺陷，一方面是来自生长过程中的晶界和褶皱，另一方面是转移过程引入的折叠，破损和撕裂。虽然研究者通过生长出厘米级石墨烯单晶，用于消除了晶界的影响，并且通过优化转移过程，消除折叠破损的影响，但是CVD石墨烯在性能上并没有本质的提升，一个重要原因便是由于褶皱的普遍存在。
褶皱的产生，是来源于CVD的高温生长环境。温度差和石墨烯与基体的热涨率差异导致石墨烯产生不可避免的褶皱。褶皱区域更容易引入一些空位缺陷，降低石墨烯的抗氧化性，导致石墨烯薄膜的质量分布不均匀。因此改进现有的CVD方法，并探索调控石墨烯褶皱的手段，从根本上消除褶皱，制备出高质量，大面积的超平整石墨烯薄膜，是实现石墨烯真正应用在高品质器件上的关键。
发明内容:
本发明的目的在于，提供一种高效消除石墨烯褶皱的新方法及CVD制备石墨烯，主要用于高品质无褶皱石墨烯的制备，或者对石墨烯的褶皱减小和彻底消除。本发明通过精确的实验调控减小和消除CVD石墨烯样品中的褶皱使得本征性质得以保留。本发明制备无褶石墨烯的尺寸达到晶片级，因此可作为一种理想方法用于器件组装及基础研究。本发明提供多种衬底上在生长同时注入质子，直接生长出超平整的无褶皱石墨烯，也包括通过传统方式生长的带有褶皱石墨烯的质子注入后处理，减小和消除褶皱的方法。
本发明的技术方案是：一种高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：利用在高温环境下的可控质子注入，通过精确控制温度环境和生成质子的氢气等离子体功率和时间，在铜、镍等各种金属及其合金，氧化硅、碳化硅等各种非金属基体上，直接生长出无褶皱的超平整石墨烯薄膜，或者消除带有褶皱的石墨烯上的褶皱；具体步骤如下：
(1)将生长基体放置于等离子体辅助化学气相沉积系统，调节好合适的反应气氛和压强，同时调整合适的耦合匹配功率，当基体加热至一定温度后保持开始启动等离子体进行反应；所述等离子体辅助化学气相沉积系统包括等离子体发生器，真空系统，加热系统等；其中等离子体发生器功率可调范围为5～1000W，真空系统可调压强10 -5～10 5Pa，系统可控加热温度范围25～1000℃；
所述使用的等离子体辅助化学气相沉积技术通过调节反应气氛和气流量、反应压强、加热温度、加热时间、等离子体功率和反应时间；反应气可为甲烷、氮气、氩气、氦气、氢气等；气流量为50～2000sccm；反应压强为1～20Pa；加热温度为500～1000℃，加热时间5min～2h；等离子体功率为5～200W，等离子体反应时间为60s～3600s。
(2)生长过程的发生与结束：加热基体到指定温度，启动等离子体的功率和反应时间，使反应发生；反应结束，关闭反应气体，样品自然降温至室温。
处理有褶皱石墨烯以减小和消除褶皱的步骤：
(1)将有褶皱石墨烯(传统化学气相沉积法方式生长在铜、镍、铂等金属，氧化硅、碳化硅等非金属基体上的石墨烯，由于热涨率差异形成的褶皱)置于等离子体辅助化学气相沉积系统，加热一定时间并辅以特定的氢气压强，同时调整适当的耦合匹配功率和反应时间，等离子体反应，可达减小和消除石墨烯褶皱；所述使用的等离子体辅助化学气相沉积技术通过调节反应的温度、压强、反应气流量、加热时间、等离子体强度 和反应时间，反应温度为100～1000℃；反应压强为1～100Pa；反应气可为氢气；气流量为5～2000sccm；加热时间为60～3600s；等离子体反应时间为60～1800s。
本发明中所述的反应衬底为铜、镍、铂、铱、钌、钨、金、银等各种金属及其合金，氧化硅、氧化铝、碳化硅等各种非金属基体。
本发明中所述等离子体辅助化学气相沉积系统包括等离子体发生器，真空系统，加热系统等。其中等离子体发生器为电感耦合的射频等离子体，功率可调范围为5～1000W，真空系统可调压强10 -5～10 5Pa，系统可控加热温度范围25～1000℃。
反应衬底为铜、镍、铂、铱、钌、钨、金、银等多种金属，氧化硅、氧化铝、碳化硅等多种非金属基体。
样品的尺寸不限，仅取决于反应系统的设计。
等离子体发生器为电感耦合等离子体发生器，功率可调范围为5W～1000W。在直接制备无褶石墨烯过程中，优选的功率为10W～20W，在等离子后处理有褶皱的石墨烯过程中，优选的功率为20W～100W。所述等离子体辅助化学气相沉积系统
所述使用的等离子体辅助化学气相沉积技术通过调节反应的温度、压强、反应气流量、加热时间、等离子体强度和反应时间，反应温度为500～1000℃；压力为1～20Pa；反应气可为碳源气体和载气，包括甲烷、氮气、氩气、氦气、氢气等；气流量为50～1000sccm；加热时间为5min～1h；等离子体功率5～200W，反应时间为60s～3600s。
所述的有褶皱石墨烯的制备是通过化学气相沉积方法，调整反应温度、压强、载气流量，生长石墨烯薄膜。反应温度600～1400℃；压强在10 -2～10 5Pa；碳源气体可为：甲烷、乙烯、乙炔、各种气态含碳有机物(液体或者固体)，气流量可为10 -5～100sccm；载气可为氢气、氮气、氦气、氩气等；气流量一般为5～5000sccm。反应时间5～3600s。
对有褶皱样品的后续处理，加热时间60～3600s，加热温度为100～1000℃；等离子体功率为10～500W，等离子体反应时间为1～30min，反应压强为1～100Pa。褶皱的高度可以有效地调控减小或者消除，对于单层石墨烯可小于等于3nm。
本发明中样品的尺寸，可以任意大小，仅取决于反应系统的设计。
本发明采用真空加热和等离子体辅助相结合，一方面，对利用CVD法在铜、镍、铂、铱、钌、金、银等金属，氧化硅、氧化铝、碳化硅等非金属为基体生长出来的带有褶皱的石墨烯，通过调节加热温度和氢气等离子体功率和时间，利用质子选择渗透的原 理，有效减小和消除褶皱，从而实现更为平整的石墨烯；另一方面，通过在CVD生长的同时加入氢等离子体，可以直接生产出无褶皱的石墨烯。此种调控，可以实现更加平整石墨烯的制备，为高性能的石墨烯单晶和薄膜的优化，提供了制备方法上的支持。
本发明通过高温环境下的质子注入，通过精确控制环境温度、气压，同时改变生成质子的氢气等离子体功率和作用时间，可以有效地减少和消除由化学气相沉积法制备石墨烯中的褶皱。该方法适用于各种衬底上生长的带有褶皱的石墨烯，如铜，铂，镍，铱，钌，钨，金，银等各种金属及其合金，氧化硅，碳化硅，氮化硅等各种非金属。本发明利用石墨烯具有质子渗透性，同时原子氢的不可渗透特性，通过可控的氢气等离子体产生出一定浓度的质子，而质子渗透石墨烯后又可以重新组合成为氢原子和氢分子，进而改变石墨烯和生长基体的层间耦合作用力，有效地控制并消除石墨烯的褶皱。直接生长或者后处理后的无褶皱石墨烯，包括有石墨烯单晶晶粒以及薄膜，尺寸可以任意，无褶皱的石墨烯表现出更高的电学性能，此种直接生长以及后处理的无褶皱石墨烯，对于高品质石墨烯在未来柔性电子器件、微纳光电器件等领域奠定了样品制备技术上的支持。
有益效果：
1.本发明采用等离子体辅助直接生长出无褶皱的石墨烯，大大提高了石墨烯的品质，石墨烯表面超平整，缺陷少，品质高。
2.本发明通过调节加热温度，加热时间，等离子体功率，等离子体反应时间，可以有效地调节石墨烯的褶皱高度和分布。
3.本发明减小和消除褶皱的过程中，不使用任何有害物质，简单高效，无褶皱石墨烯可以在极短时间内产生。
4.本发明是一个普适的方法，可以在铜、镍、铂、铱、钌、钨、金、银等各种金属及其合金，氧化硅、氧化铝、碳化硅等各种非金属基体上使用。
总之，本发明通过高温加热以及氢气等离子体下的质子注入，通过精确控制加热温度和等离子体功率，能够有效的减少和消除由化学气相沉积法石墨烯中的褶皱。不仅可以在多种基体上直接生长出超平整无褶皱的高质量石墨烯薄膜，同时也可以通过后处理的方式减小和消除普通CVD法生长的石墨烯褶皱。超平整、无褶皱的石墨烯薄膜尺寸可以任意大小，仅取决于生长系统的设计。此种无褶皱石墨烯的可控获取，对提升CVD法生长石墨烯的性能，并为实现在未来柔性电子器件、高性能电子、光电器件等领域的应用奠定了制备技术上的支持。
本发明方法适用于各种衬底上生长的带有褶皱的石墨烯，如铜，铂，镍，铱，钌，钨，金，银等各种金属及其合金，氧化硅，碳化硅，氮化硅等各种非金属。本发明利用石墨烯具有质子渗透性，同时原子氢的不可渗透特性，通过可控的氢气等离子体产生出一定浓度的质子，而质子渗透石墨烯后又可以重新组合成为氢原子和氢分子，进而改变石墨烯和生长基体的层间耦合作用力，有效地控制并消除石墨烯的褶皱。本发明涉及到多种衬底上在生长同时注入质子，直接生长出超平整的无褶皱石墨烯，也包括通过传统方式生长的带有褶皱石墨烯的质子注入后处理，减小和消除褶皱。直接生长或者后处理后的无褶皱石墨烯，包括有石墨烯单晶晶粒以及薄膜，尺寸可以任意，无褶皱的石墨烯表现出更高的电学性能，此种直接生长以及后处理的无褶皱石墨烯，对于高品质石墨烯在未来柔性电子器件、微纳光电器件等领域奠定了样品制备技术上的支持。
附图说明:
图1.在铜基体上减小和去除石墨烯褶皱的示意图。
图2.在铜基体上生长的无褶皱石墨烯：(a)为20厘米的无褶皱石墨烯薄膜图片；(b)对应的原子力显微镜图片；(c)为(b)在黑色实线标定位置的高度图；(d)为无褶皱石墨烯的显微拉曼光谱。
图3.转移到带有氧化层的硅片表面的无褶皱石墨烯薄膜：(a)光学照片；(b)原子力显微镜照片；(c)来自(b)中黑色实线标记位置的高度图。
图4.有褶皱石墨处理前测量的原子力显微镜图片。
图5.图4通过对有褶皱石墨烯进行后处理，在相同位置测量的原子力显微镜图片(无褶皱)。
具体实施方式:
该方法利用高温加热和氢气等离子体注入，通过精确控制加热温度和调整等离子体功率等方式，从而在铜、镍等各种金属及其合金，氧化硅、碳化硅等多种金属、非金属基体上生长出无褶皱的超平整石墨烯薄膜。具体实施例如下：
实施例1
通过等离子体辅助在铜基体上生长出无褶皱的石墨烯，具体为：平滑的铜薄膜(镀 在蓝宝石上)，放置在管式炉中加热至1000℃并维持40分钟，获得比较平滑的铜表面。将铜基体放入等离子体辅助化学气相沉积系统中，通入氢气和甲烷，比例为20:1(总气流量为200sccm)，通过调压阀门稳定反应室压强为10Pa，加热至500～800℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为10～50W，通过改变等离子体功率和时间来控制石墨烯薄膜的晶粒尺寸和生长速率，一般生长2～5分钟就能获得单层、无褶皱的石墨烯薄膜。生长完成后自然降温，待温度降至近室温时关闭气体。
生长的石墨烯样品，利用光学显微镜观察样品表面均匀性，利用原子力显微镜观察样品表面粗糙度等信息，利用拉曼光谱判断石墨烯的晶体质量。
实施例2
与实施例1不同之处在于：
通过等离子体辅助在铜基体上生长出无褶皱的石墨烯，具体为：平滑的铜薄膜(镀在蓝宝石上)，放置在管式炉中加热至1000℃并维持40分钟，获得比较平滑的铜表面。将铜基体放入等离子体辅助化学气相沉积系统中，通入氢气和甲烷，比例为20:1(本实施例中，总的气流量可以使用50～1000sccm)，通过调压阀门稳定反应室压强为10Pa，加热至500～800℃，并保持30m分钟(本实施例中，保持时间可以在5min～2h之间)。启动电感耦合等离子体发生器，调节功率为10～50W，通过改变等离子体功率和时间来控制石墨烯薄膜的晶粒尺寸和生长速率，一般生长2～5分钟就能获得单层、无褶皱的石墨烯薄膜(本实施例中可以调整生长时间在60s～3600s之间，可以得到无褶的石墨烯晶粒和单层无褶石墨烯薄膜)。生长完成后自然降温，待温度降至近室温时关闭气体。
生长的石墨烯样品，利用光学显微镜观察样品表面均匀性，利用原子力显微镜观察样品表面粗糙度等信息，利用拉曼光谱判断石墨烯的晶体质量。
实施例3
与实施例1不同之处在于：
通过等离子体辅助在镍基体上生长出无褶皱的石墨烯，(本实施例中，衬底使用镍、铂、金、银、铑、铱、钌等其他金属及合金薄膜，以镍为例)，具体为：平滑的镍薄膜(镀在蓝宝石上)，放置在管式炉中加热至1000℃并维持40分钟，获得比较平滑的镍表面。将镍基体放入等离子体辅助化学气相沉积系统中，通入氢气和甲烷，比例为40:1(总气流量为200sccm)，通过调压阀门稳定反应室压强为10Pa，加热至500～800℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为10～50W，通过改变 等离子体功率和时间来控制石墨烯薄膜的晶粒尺寸和生长速率，一般生长2～5分钟就能获得单层、无褶皱的石墨烯薄膜。生长完成后自然降温，待温度降至近室温时关闭气体。
制备的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度等信息，利用拉曼光谱判断样品的晶体质量。
实施例4
与实施例1不同之处在于：
通过等离子体辅助在氧化铝基体上生长出无褶皱的石墨烯，(本实施例中，衬底使用氧化铝、氧化硅、碳化硅、氧化镁、硅、六方氮化硼等非金属基体，以氧化铝例)，具体为：将氧化铝基体放入等离子体辅助化学气相沉积系统中，通入氢气和甲烷，比例为10:1(总气流量为200sccm)，通过调压阀门稳定反应室压强为10Pa，加热至800～1000℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为50～200W，通过改变等离子体功率和时间来控制石墨烯薄膜的晶粒尺寸和生长速率，一般生长5～10分钟就能获得单层、无褶皱的石墨烯薄膜。生长完成后自然降温，待温度降至近室温时关闭气体。
制备的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度等信息，利用拉曼光谱判断样品的晶体质量。
实施例5
与实施例4不同之处在于：
通过等离子体辅助在氧化铝基体上生长出无褶皱的石墨烯，(本实施例中，衬底使用氧化铝、氧化硅、碳化硅、氧化镁、硅、六方氮化硼等非金属基体，以氧化铝例)，具体为：将氧化铝基体放入等离子体辅助化学气相沉积系统中，通入氢气和甲烷，比例为10:1(本实施例中可以调整气流总量在50～1000sccm之间)，通过调压阀门稳定反应室压强为10Pa(本实施例中使用压强1～20Pa)，加热至800～1000℃，并保持30分钟(本实施例中调整保温时间5min～2h)。启动电感耦合等离子体发生器，调节功率为50～200W，通过改变等离子体功率和时间来控制石墨烯薄膜的晶粒尺寸和生长速率，一般生长5～10分钟就能获得单层、无褶皱的石墨烯薄膜。生长完成后自然降温，待温度降至近室温时关闭气体
制备的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜 观察样品表面粗糙度等信息，利用拉曼光谱判断样品的晶体质量。
实施例6(有褶石墨烯制备的补充实施例6和7)
与实施例1不同之处在于：
通过高温加热并辅以等离子体，减小和消除生长在铜基体上石墨烯的褶皱，具体为：首先要在铜基体上生长出有褶皱的石墨烯薄膜，本实施例中，有褶皱石墨烯是以甲烷为碳源常压生长：将铜基地放入管式炉中，通入氩气和氢气，比例为10:1,总气流量为500sccm，然后加热至1000℃并保持40min退火，然后通入百分之一稀释的甲烷5～50sccm，常压生长600～3600s，然后自然降温得到有褶皱石墨烯。再将有褶的石墨烯放置在等离子体辅助化学气相沉积系统中，通入氢气，通过调压阀门稳定反应室压强为10Pa，加热至500～800℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为10～50W，一般处理1～5分钟就能有效降低和去除石墨烯薄膜中的褶皱。处理完成后自然降温，待温度降至近室温时关闭气体。
处理后的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度，褶皱等信息，利用拉曼光谱判断石墨烯的晶体质量。
实施例7
与实施例6不同之处在于：
通过高温加热并辅以等离子体，减小和消除生长在铜基体上石墨烯的褶皱，具体为：首先要在铜基体上生长出有褶皱的石墨烯薄膜，(本实施例中，碳源为乙烯、乙炔、各种气态含碳有机物(液体或者固体)，反应压强在10 -2～10 5Pa之间，载气为氢气、氦气、氩气等)：以乙烯做为碳源为例，反应压强为10 -1pa，总气流量10sccm，反应温度800℃，生长时间为600s，在铜衬底上得到有褶皱石墨烯薄膜。再将有褶的石墨烯放置在等离子体辅助化学气相沉积系统中，通入氢气，通过调压阀门稳定反应室压强为10Pa，加热至500～800℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为10～50W，一般处理1～5分钟就能有效降低和去除石墨烯薄膜中的褶皱。处理完成后自然降温，待温度降至近室温时关闭气体。
处理后的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度，褶皱信息，利用拉曼光谱判断石墨烯的晶体质量
实施例8
与实施例6不同之处在于：
通过高温加热并辅以等离子体，减小和消除生长在镍基体上石墨烯的褶皱，(本实施例中，衬底使用镍、铂、金、银、铑、铱、钌等其他金属及合金薄膜，以镍为例)，具体为：首先将已经生长在镍基体上带有褶皱的石墨烯薄膜，放置在等离子体辅助化学气相沉积系统中，通入氢气，通过调压阀门稳定反应室压强为10Pa，加热至500～800℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为10～50W，一般处理1～5分钟就能有效降低和去除石墨烯薄膜中的褶皱。处理完成后自然降温，待温度降至近室温时关闭气体。
处理后的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度，褶皱等信息，利用拉曼光谱判断石墨烯的晶体质量。
实施例9
对有褶皱样品的后续处理，加热时间60～3600s，加热温度为100～1000℃；等离子体功率为10～500W，等离子体反应时间为1～30min，反应压强为1～100Pa。与实施例6不同之处具体在于：通过高温加热并辅以等离子体，减小和消除生长在氧化铝基体上石墨烯的褶皱，(本实施例中，衬底使用氧化铝、氧化硅、碳化硅、氧化镁、硅、六方氮化硼等非金属基体，以氧化铝例)，具体为：首先将已经生长在氧化铝基体上带有褶皱的石墨烯薄膜，放置在等离子体辅助化学气相沉积系统中，通入氢气，通过调压阀门稳定反应室压强为10Pa，加热至800～1000℃，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为50～200W，一般处理5～10分钟就能有效降低和去除石墨烯薄膜中的褶皱。处理完成后自然降温，待温度降至近室温时关闭气体。
处理后的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度，褶皱等信息，利用拉曼光谱判断石墨烯的晶体质量。
实施例10
与实施例9不同之处在于：
通过高温加热并辅以等离子体，减小和消除生长在氧化铝基体上石墨烯的褶皱，(本实施例中，衬底使用氧化铝、氧化硅、碳化硅、氧化镁、硅、六方氮化硼等非金属基体，以氧化铝例)，具体为：首先将已经生长在氧化铝基体上带有褶皱的石墨烯薄膜，放置在等离子体辅助化学气相沉积系统中，通入氢气，通过调压阀门稳定反应室压强为10Pa，加热至300℃(本实施例中降低加热温度范围在100～500℃)，并保持1～10分钟。启动电感耦合等离子体发生器，调节功率为300W(本实施例中增大反应功率，范围在 200～500W之间)，处理20分钟(本实施例中延长处理时间)就能有效降低和去除石墨烯薄膜中的褶皱。处理完成后自然降温，待温度降至近室温时关闭气体。
处理后的样品，利用光学显微镜观察样品表面均匀性与破损程度，利用原子力显微镜观察样品表面粗糙度，褶皱等信息，利用拉曼光谱判断石墨烯的晶体质量。
如图1所示，在铜基体上减小和去除石墨烯褶皱的示意图。
如图2所示，在铜衬底上直接生长无褶皱石墨烯：(a)为10厘米的无褶皱石墨烯薄膜图片；(b)对应的原子力显微镜图片；(c)为(b)在黑色实线标定位置的高度图；(d)为无褶皱石墨烯的显微拉曼光谱。
如图3所示，转移到带有氧化层的硅片表面的无褶皱石墨烯薄膜：(a)光学照片；(b)原子力显微镜照片；(c)来自(b)中黑色实线标记位置的高度图。
如图4、5所示对比，通过对有褶皱石墨烯进行后处理，在相同位置测量的原子力显微镜图片比较。

Claims (8)

  1. 一种高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：利用在高温环境下的可控质子注入，通过精确控制温度环境和生成质子的氢气等离子体功率和时间，在铜、镍等各种金属及其合金，氧化硅、碳化硅等各种非金属基体上，直接生长出无褶皱的超平整石墨烯薄膜，或者消除带有褶皱的石墨烯上的褶皱；
    具体步骤如下：
    (1)将生长基体放置于等离子体辅助化学气相沉积系统，调节好合适的反应气氛和压强，同时调整合适的耦合匹配功率，当基体加热至一定温度后保持开始启动等离子体进行反应；所述等离子体辅助化学气相沉积系统包括等离子体发生器，真空系统，加热系统等；其中等离子体发生器功率可调范围为5～1000W，真空系统可调压强10 -5～10 5Pa，系统可控加热温度范围25～1000℃；
    所述使用的等离子体辅助化学气相沉积技术通过调节反应气氛和气流量、反应压强、加热温度、加热时间、等离子体功率和反应时间；反应气可为甲烷、氮气、氩气、氦气、氢气等；气流量为50～2000sccm；反应压强为1～20Pa；加热温度为500～1000℃，加热时间5min～2h；等离子体功率为5～200W，等离子体反应时间为60s～3600s；
    (2)生长过程的发生与结束：加热基体到指定温度，启动等离子体的功率和反应时间，使反应发生；反应结束，关闭反应气体，样品自然降温至室温。
  2. 一种高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：处理有褶皱石墨烯以减小和消除褶皱的步骤：
    (1)将有褶皱石墨烯(传统化学气相沉积法方式生长在铜、镍、铂等金属，氧化硅、碳化硅等非金属基体上的石墨烯，由于热涨率差异形成的褶皱)置于等离子体辅助化学气相沉积系统，加热一定时间并辅以特定的氢气压强，同时调整适当的耦合匹配功率和反应时间，等离子体反应，可达减小和消除石墨烯褶皱；所述使用的等离子体辅助化学气相沉积技术通过调节反应的温度、压强、反应气流量、加热时间、等离子体强度和反应时间，反应温度为100～1000℃；反应压强为1～100Pa；反应气可为氢气；气流量为5～2000sccm；加热时间为60～3600s；等离子体反应时间为60～1800s。
  3. 根据权利要求1或2所述的高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：反应衬底为铜、镍、铂、铱、钌、钨、金、银等多种金属，氧化硅、氧化铝、碳化硅等多种非金属基体。
  4. 根据权利要求1或2所述的高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：其中等离子体发生器为电感耦合的射频等离子体，功率可调范围为5～1000W，真空系统可调节压强10 -5～10 5Pa，系统可控加热温度范围25～1000℃。
  5. 根据权利要求1所述的高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：所述使用的等离子体辅助化学气相沉积技术通过调节反应的温度、压强、反应气流量、加热时间、等离子体强度和反应时间，反应温度为500～1000℃；压力为1～20Pa；反应气可为甲烷、氮气、氩气、氦气、氢气等；气流量为50～1000sccm；加热时间为5min～1h；等离子体功率5～200W，反应时间为60s～3600s。
  6. 根据权利要求2所述的高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：所述的有褶皱石墨烯的制备是通过化学气相沉积方法，通过调整反应温度、压强、载气流量，生长出有褶皱石墨烯薄膜；反应温度600～1400℃；压强在10 -2～10 5Pa；碳源气体可为：甲烷、乙烯、乙炔、各种气态含碳有机物(液体或者固体)，气流量可为10 -5～100sccm；载气为氢气、氮气、氦气、氩气等；气流量一般为5～5000sccm。反应时间5～3600s。
  7. 根据权利要求2所述的高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：对有褶皱样品的后续处理，加热时间60～3600s，加热温度为100～1000℃；等离子体功率为10～500W，等离子体反应时间为1～30min，反应压强为1～100Pa。
  8. 根据权利要求1或2所述的高效消除化学气相沉积法石墨烯褶皱的方法，其特征在于：褶皱的高度可以有效地调控减小或者消除，对于单层石墨烯可小于等于3nm。样品的尺寸不限。
PCT/CN2019/127803 2019-02-20 2019-12-24 一种高效消除化学气相沉积法石墨烯褶皱的方法 Ceased WO2020168819A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074694A (zh) * 2022-07-01 2022-09-20 常州第六元素半导体有限公司 一种石墨烯薄膜制备方法
CN117446790A (zh) * 2022-07-19 2024-01-26 中国科学院金属研究所 一种在非金属基体表面低温生长石墨烯的方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824038B (zh) * 2019-02-20 2022-03-25 南京大学 一种高效消除化学气相沉积法石墨烯褶皱的方法
US12389805B2 (en) * 2019-11-14 2025-08-12 National Institutes for Quantum Science and Technology Layered structure, magnetoresistive device using the same, and method of fabricating layered structure
WO2021133158A1 (en) * 2019-12-23 2021-07-01 Mimos Berhad Method of forming single layer nitrogen-doped graphene
CN114472522B (zh) * 2022-01-26 2024-09-27 重庆墨希科技有限公司 等离子辅助制备高导电石墨烯金属复合材料的方法及装置
CN115285982B (zh) * 2022-07-29 2024-04-26 西北有色金属研究院 一种单晶硅表面等离子辅助cvd制备石墨烯膜层的方法
US20240052481A1 (en) * 2022-08-09 2024-02-15 City University Of Hong Kong Method for direct formation of origami 3d graphene on copper foil using chemical vapor deposition
CN116426897B (zh) * 2023-03-21 2025-07-15 中国科学院工程热物理研究所 一种微通道散热器表面防腐处理的方法
US20240339324A1 (en) * 2023-04-05 2024-10-10 Applied Materials, Inc. Atmospheric Pressure Plasma for Substrate Annealing
CN117756104B (zh) * 2023-11-20 2025-11-07 宁波大学 一种石墨烯形貌控制方法、sers薄膜及检测应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260858A (zh) * 2010-05-26 2011-11-30 中国科学院物理研究所 一种在各种基底上直接生长石墨烯的方法
JP2014024700A (ja) * 2012-07-26 2014-02-06 National Institute Of Advanced Industrial & Technology グラフェンロールフィルム、グラフェンロールフィルムの成膜方法及び成膜装置
CN105110324A (zh) * 2015-08-18 2015-12-02 中国科学院上海微系统与信息技术研究所 一种制备无褶皱的石墨烯的方法
KR20160106869A (ko) * 2015-03-03 2016-09-13 이윤택 기판 성장 그래핀의 제조방법 및 기판 성장 그래핀
GB2539016B (en) * 2015-06-03 2017-12-06 Rd Graphene Ltd Manufacture of graphene by plasma-enhanced CVD
CN108502873A (zh) * 2018-06-26 2018-09-07 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 一种高质量、少缺陷、结构均匀的石墨烯的制备方法
CN109824038A (zh) * 2019-02-20 2019-05-31 南京大学 一种高效消除化学气相沉积法石墨烯褶皱的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9328413B2 (en) * 2011-07-22 2016-05-03 Shanghai Institute Of Microsystem And Information Technology, Chinese Academy Of Sciences Method for preparing graphene nanoribbon on insulating substrate
CN104334495A (zh) * 2012-05-17 2015-02-04 新加坡国立大学 生长均匀、大规模的多层石墨烯膜的方法
KR20200003258A (ko) * 2013-01-14 2020-01-08 캘리포니아 인스티튜트 오브 테크놀로지 그라펜을 형성시키는 방법 및 시스템
GB201410639D0 (en) * 2014-06-13 2014-07-30 Fgv Cambridge Nanosystems Ltd Apparatus and method for plasma synthesis of graphitic products including graphene
CN105274500A (zh) * 2015-10-24 2016-01-27 复旦大学 等离子体增强化学气相沉积制备石墨烯的方法
US11124870B2 (en) * 2017-06-01 2021-09-21 Kuk-Il Graphene Co., Ltd. Transfer-free method for producing graphene thin film

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260858A (zh) * 2010-05-26 2011-11-30 中国科学院物理研究所 一种在各种基底上直接生长石墨烯的方法
JP2014024700A (ja) * 2012-07-26 2014-02-06 National Institute Of Advanced Industrial & Technology グラフェンロールフィルム、グラフェンロールフィルムの成膜方法及び成膜装置
KR20160106869A (ko) * 2015-03-03 2016-09-13 이윤택 기판 성장 그래핀의 제조방법 및 기판 성장 그래핀
GB2539016B (en) * 2015-06-03 2017-12-06 Rd Graphene Ltd Manufacture of graphene by plasma-enhanced CVD
CN105110324A (zh) * 2015-08-18 2015-12-02 中国科学院上海微系统与信息技术研究所 一种制备无褶皱的石墨烯的方法
CN108502873A (zh) * 2018-06-26 2018-09-07 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 一种高质量、少缺陷、结构均匀的石墨烯的制备方法
CN109824038A (zh) * 2019-02-20 2019-05-31 南京大学 一种高效消除化学气相沉积法石墨烯褶皱的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074694A (zh) * 2022-07-01 2022-09-20 常州第六元素半导体有限公司 一种石墨烯薄膜制备方法
CN117446790A (zh) * 2022-07-19 2024-01-26 中国科学院金属研究所 一种在非金属基体表面低温生长石墨烯的方法

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