WO2012167701A1

WO2012167701A1 - Chemical vapor deposition method for producing monolayer and multilayer graphene

Info

Publication number: WO2012167701A1
Application number: PCT/CN2012/076194
Authority: WO
Inventors: 瞿研
Original assignee: 无锡第六元素高科技发展有限公司
Priority date: 2011-06-09
Filing date: 2012-05-29
Publication date: 2012-12-13
Also published as: CN102220566A

Abstract

The present invention relates to a method of producing monolayer and multilayer graphene via chemical vapor deposition. The method takes place in a reducing atmosphere where carbon gas is passed through temperatures that graduate from high to low and accumulates atop a substrate from which monolayer and/or multilayer graphene is obtained; the reducing atmosphere being a hydrogen atmosphere. The chemical vapor deposition method for obtaining monolayer and multilayer graphene provided by the present invention is operationally simple, has easily controllable operational conditions, and does not require the preparation of a catalyst; graphene product obtained from the process have measurements reaching over a centimeter, and a low defect peak. The graphene product has advantageously high crystal quality and good light transmission properties. The thickness of monolayer and multilayer graphene can be controlled, and single-atomic-layer graphene is easily obtained.

Description

一种化学气相沉积制备单层和多层石墨烯的方法 Method for preparing single layer and multilayer graphene by chemical vapor deposition

技术领域 Technical field

本发明涉及石墨烯材料的制备技术领域，具体地涉及一种化学气相沉积制备单层和多层石墨烯的方法。 The present invention relates to the technical field of preparation of graphene materials, and in particular to a method for preparing single layer and multilayer graphene by chemical vapor deposition.

背景技术 Background technique

石墨烯，英文名 Gmphene, 是碳原子按照六角排列而成的二维晶格结构。作为单层碳原子平面材料，石墨烯可以通过剥离石墨材料而得到。这种石墨晶体薄膜自 2004年被曼彻斯特大学的科学家发现之后，石墨烯就成为科学界和工业界关注的焦点。石墨烯的厚度只有 0.335nm，不仅是己知材料中最薄的一种，还非常牢固坚硬；作为单质，他在室温下传递电子的速度比已知所有的导体和半导体都快（石墨烯中电子的迁移速度达到了光速的 1/300)。由于石墨烯的特殊原子结构，其中载流子（电子和空穴）的行为必须用相对论量子力学 (Relativistic Quantum Mechanics) 才能描绘。由于其高电子迁移率以及高透光率，石墨烯可能被应用在各种信息技术领域，例如作为透明导电电极应用在平板显示器上，或者作为沟道层应用在高频 /射频晶体管上。同时，作为单层碳原子结构，石墨烯的理论比表面积高达 2630m²/g。如此高的比表面积使得以基于石墨烯的材料成为极有前途的能量储存活性材料，使得石墨烯材料有可能在储氢、新型锂离子电池、超级电容器或者燃料电池得到应用。 Graphene, the English name Gmphene, is a two-dimensional lattice structure in which carbon atoms are arranged in hexagons. As a single-layer carbon atom planar material, graphene can be obtained by peeling off a graphite material. Since the graphite crystal film was discovered by scientists at the University of Manchester in 2004, graphene has become the focus of attention in the scientific and industrial circles. Graphene has a thickness of only 0.335 nm, which is not only the thinnest of the known materials, but also very strong and hard. As a simple substance, it transmits electrons at room temperature faster than all known conductors and semiconductors (graphene The migration speed of electrons reaches 1/300 of the speed of light). Due to the special atomic structure of graphene, the behavior of carriers (electrons and holes) must be characterized by Relativistic Quantum Mechanics. Due to its high electron mobility and high light transmittance, graphene may be used in various information technology fields, for example, as a transparent conductive electrode for flat panel displays, or as a channel layer for high frequency/RF transistors. Meanwhile, as a single layer structure of carbon atoms, the theoretical specific surface area of up graphene 2630m ² / g. Such a high specific surface area makes the graphene-based material a promising energy storage active material, making it possible to use graphene materials in hydrogen storage, new lithium ion batteries, supercapacitors or fuel cells.

目前有以下几种方法制备这种特殊的材料： There are several ways to prepare this special material:

1. 轻微摩擦法或撕胶带法（粘贴 HOPG (高定向热解石墨）） 1. Slight rubbing or tearing tape method (paste HOPG (highly oriented pyrolytic graphite))

这种方法简单易行，容易得到高质量的石墨烯。但是产率极低，在一块 Si 衬底上通常只能得到若干片微米见方的石墨烯。因此这种方法只适用于实验室制备石墨烯，不适用于工业化大规模生产。 This method is simple and easy to obtain high quality graphene. But the yield is extremely low, in a piece of Si Usually only a few micrometers of graphene are obtained on the substrate. Therefore, this method is only suitable for the preparation of graphene in the laboratory, and is not suitable for industrial mass production.

2. 加热 SiC法 2. Heating SiC method

该法是通过加热单晶 6H-SiC脱除 Si，在单晶（0001 )面上分解出石墨烯片层。具体过程是：将经氧气或氢气刻蚀处理得到的样品在高真空下通过电子轰击加热，除去氧化物。用俄歇电子能谱确定表面的氧化物完全被移除后，将样品加热使之温度升高至 1250-1450°C后恒温 1分钟到 20分钟，从而形成极薄的石墨层，经过几年的探索， Berger 等人已经能可控地制备出单层或是多层石墨烯。由于其厚度由加热温度决定，制备大面积具有单一厚度的石墨烯比较困难。 In this method, Si is removed by heating single crystal 6H-SiC, and a graphene sheet is decomposed on the single crystal (0001) plane. The specific process is as follows: A sample obtained by etching with oxygen or hydrogen is heated by electron bombardment under high vacuum to remove oxides. After the Auchen electron spectroscopy is used to confirm that the oxide on the surface is completely removed, the sample is heated to raise the temperature to 1250-1450 ° C and then thermostated for 1 minute to 20 minutes to form a very thin graphite layer. Exploration, Berger et al. have been able to controllably prepare single or multiple layers of graphene. Since the thickness is determined by the heating temperature, it is difficult to prepare a graphene having a single thickness in a large area.

该方法可以实现大尺寸，高质量石墨烯制备，是一种对实现石墨烯器件的实际应用非常重要的制备方法，缺点是 SiC过于昂贵，并且得到的石墨烯难以转移到其他衬底上。 The method can realize large-size, high-quality graphene preparation, and is a preparation method which is very important for realizing the practical application of the graphene device. The disadvantage is that SiC is too expensive, and the obtained graphene is difficult to transfer to other substrates.

3. 化学分散法 3. Chemical dispersion method

氧化石墨是石墨在 ¾S0₄、 HN0₃、 HC10₄等强氧化剂的作用下，或电化学过氧化作用下，经水解后形成的。氧化石墨同样是一层状共价化合物，层间距离大约为 0.8nm (石墨为 0.335nm)，依制备方法而异。一般认为，氧化石墨中含有 -C-OH、 -C-0-C, 甚至 -COOH等基团。和石墨不同，由于极性基团的存在，氧化石墨片层具有较强的亲水或极性溶剂的特性。因此，氧化石墨在外力，如超声波的作用下在水中或其他极性溶剂中可以发生剥离，形成单层氧化石墨烯 (Graphene Oxide )。制得氧化石墨烯后，再通过化学还原使所制氧化石墨烯脱氧重新石墨化，保持其几何形貌时可恢复部分其导电性。 Graphite oxide is formed by the hydrolysis of graphite under the action of strong oxidants such as 3⁄4S0 ₄ , HN0 ₃ , HC10 ₄ or by electrochemical peroxidation. Graphite oxide is also a layered covalent compound with a interlayer distance of about 0.8 nm (graphite is 0.335 nm), which varies depending on the preparation method. It is considered that the graphite oxide contains a group such as -C-OH, -C-0-C, or even -COOH. Unlike graphite, the graphite oxide sheet has a strong hydrophilic or polar solvent property due to the presence of polar groups. Therefore, the graphite oxide can be peeled off in water or other polar solvent by an external force such as ultrasonic waves to form a single layer of graphene oxide (Graphene Oxide). After the graphene oxide is obtained, the graphene oxide is deoxidized and re-graphitized by chemical reduction, and the conductivity of the portion can be restored when the geometrical morphology is maintained.

该方法在氧化和还原过程中将天然石墨粉解离成单层石墨。虽然在氧化还原过程中只是部分还原其导电性（破坏了石墨烯本身的高电子迁移率），但是其产品具有相当高的粉末比表面积（>700m²/g)，且过程相对简单，因此该方法比较适合工业化大规模生产石墨烯材料。但是在氧化还原过程中只是部分还原其导电性（破坏了石墨烯本身的高电子迁移率）。 The method dissociates natural graphite powder into a single layer of graphite during oxidation and reduction. Although it only partially reduces its conductivity during the redox process (destroying the high electron mobility of graphene itself), The product has a relatively high powder specific surface area (>700 m ² /g) and the process is relatively simple, so the method is more suitable for industrial large-scale production of graphene materials. However, it is only partially reduced in conductivity during the redox process (destroying the high electron mobility of the graphene itself).

4、化学气相沉积法（CVD， Chemical Vapor Deposition) 4, chemical vapor deposition (CVD, Chemical Vapor Deposition)

利用甲垸等含碳化合物作为碳源，通过其在基体表面的高温分解生长石墨烯。任文才在 "石墨烯的化学气相沉积法制备"中给出了 CVD法中，石墨烯的生长机理：（1 ) 渗碳析碳机理：对于镍等具有较高溶碳量的金属基体，碳源裂解产生的碳原子在高温时渗入金属机体内，在降温时再从其内部析出成核，进而生长成石墨烯；（2 ) 表面生长机制：对于铜等具有较低溶碳量的金属基体，高温下气态碳源裂解生成的碳原子吸附于金属表面，进而成核生长成 "石墨烯岛"，并通过 "石墨烯岛" 的二维长大合并得到连续的石墨烯薄膜。（石墨烯的化学气相沉积法制备，任文才等，新型炭材料， 2011年 02月，第 26卷第 1期） CN101285175 公开了一种石墨烯的制备方法。该方法是采用化学气相沉积法制备石墨烯，包括如下歩骤：将带有催化剂的衬底放入无氧的反应器中，使衬底的温度达到 500-1200°C，然后向所述反应器中通入含碳物质，得到石墨烯; 其中，所述催化剂为金属或金属化合物。该发明所述的制备石墨烯的方法，需要先在衬底上沉积催化剂，待沉积得到石墨烯后需要再次将催化剂除去，歩骤繁琐。 A carbonaceous compound such as formazan is used as a carbon source, and graphene is grown by pyrolysis on the surface of the substrate. Ren Wencai gave the growth mechanism of graphene in CVD method in "Preparation of Graphene by Chemical Vapor Deposition": (1) Carburizing and Carburizing Mechanism: For metal matrix with high carbon content such as nickel, carbon The carbon atoms generated by the source cracking penetrate into the metal body at a high temperature, and then nucleate out from the inside when the temperature is lowered, and then grow into graphene; (2) Surface growth mechanism: a metal matrix having a lower carbon content such as copper The carbon atoms generated by the cracking of the gaseous carbon source at high temperature are adsorbed on the surface of the metal, and then nucleated to form a "graphene island", and a two-dimensional growth of the "graphene island" is combined to obtain a continuous graphene film. (Preparation of Graphene by Chemical Vapor Deposition, Ren Wencai et al., New Carbon Materials, 2011, February, Vol. 26, No. 1) CN101285175 discloses a method for preparing graphene. The method comprises the steps of preparing a graphene by chemical vapor deposition, comprising the steps of: placing a substrate with a catalyst in an oxygen-free reactor, bringing the temperature of the substrate to 500-1200 ° C, and then reacting to the reaction. A carbonaceous material is introduced into the apparatus to obtain graphene; wherein the catalyst is a metal or a metal compound. The method for preparing graphene according to the invention requires that a catalyst be deposited on the substrate first, and the catalyst needs to be removed again after the graphene is deposited, which is cumbersome.

如何开发一种制备方法简单、易控、缺陷低、透光性好、尺寸大且厚度单一可控的石墨烯是本领域的一个技术问题。 How to develop a graphene with simple preparation method, easy control, low defect, good light transmittance, large size and single thickness controllable is a technical problem in the art.

发明内容 Summary of the invention

针对现有技术的不足，本发明的目的之一在于提供一种制备超大面积的厚度可控的单层或多层石墨烯薄膜的方法。所述方法是在还原气氛中，将碳源气体通过从高温逐渐降温的方式沉积在衬底上，从而得到单层和 /或多层石墨烯；所述还原气氛为氢气气氛。 In view of the deficiencies of the prior art, it is an object of the present invention to provide a method of preparing a super-large area thickness controllable single or multi-layer graphene film. The method is to reduce the carbon source gas in a reducing atmosphere The body is deposited on the substrate by gradually decreasing the temperature from the high temperature, thereby obtaining a single layer and/or a plurality of layers of graphene; the reducing atmosphere is a hydrogen atmosphere.

现有技术表明，石墨烯的 CVD生长主要涉及三个方面：碳源、生长基体（衬底）和生长条件（气压、载体、温度等）。（石墨烯的化学气相沉积法制备，任文才等，新型炭材料， 2011年 02月，第 26卷第 1期） The prior art shows that CVD growth of graphene mainly involves three aspects: carbon source, growth substrate (substrate) and growth conditions (air pressure, carrier, temperature, etc.). (Preparation of Graphene by Chemical Vapor Deposition, Ren Wencai et al., New Carbon Materials, February 2011, Vol. 26, No. 1)

在本发明中，碳源为气态碳源。优选地，本发明所述的碳源气体为只含有碳原子和氢原子的有机气体，本领域技术人员能够获知的任何一种只含有。、 H 元素的气体均可用于本发明，本发明优选 C1-C4的垸烃、 C2-C4的烯烃、 C2-C3 的炔烃中的任意 1种或至少 2种的组合，其中， C1-C4的垸烃的实例有甲垸、乙垸、丙垸、环丙垸、正丁垸、异丁垸、甲基环丙垸或环丁垸等； C2-C4的烯烃的实例有乙烯、丙烯、正丁烯、异丁烯、 1,3-丁二烯、 1,2-丁二烯等； C2-C3 的炔烃的实例有乙炔、丙炔、 1-丁炔、 2-丁炔等，所述组合例如甲垸 /乙垸、乙炔 /1,2- 丁二烯 /正丁垸、丙炔 /丙垸、正丁垸 /1,3-丁二烯 /2-丁炔等。 In the present invention, the carbon source is a gaseous carbon source. Preferably, the carbon source gas of the present invention is an organic gas containing only carbon atoms and hydrogen atoms, and any one known to those skilled in the art contains only one. The gas of the H element may be used in the present invention, and the present invention preferably has any one or a combination of at least two of a C1-C4 terpene hydrocarbon, a C2-C4 olefin, and a C2-C3 alkyne, wherein C1-C4 Examples of the terpene hydrocarbons include formazan, ethyl hydrazine, propylene sulfonium, cyproterone, n-butyl hydrazine, isobutyl hydrazine, methylcyclopropene or cyclobutyl hydrazine; and examples of the C2-C4 olefin are ethylene, propylene, N-butene, isobutylene, 1,3-butadiene, 1,2-butadiene, etc.; examples of the C2-C3 alkyne are acetylene, propyne, 1-butyne, 2-butyne, etc. Combinations such as formazan/acetamidine, acetylene/1,2-butadiene/n-butane, propyne/propionamidine, n-butylene/1,3-butadiene/2-butyne, and the like.

在 CVD沉积制备石墨烯的过程中，碳源的选择在很大程度上决定了石墨烯的生长温度等操作条件，本发明在考虑了碳源气体的分解温度、分解速度和分解产物的因素后，进一歩优选甲垸、乙垸、乙烯、乙炔、丙垸、正丁烯、异丁烯、 1,2-丁二烯、 1,3-丁二烯、顺丁二烯、反丁二烯、正丁垸、异丁垸、丙烯、环丙垸中的任意 1种或至少 2种的组合作为本发明的碳源气体，特别优选甲垸作为本发明的碳源气体。 In the process of preparing graphene by CVD deposition, the selection of the carbon source largely determines operating conditions such as the growth temperature of graphene, and the present invention considers the decomposition temperature, decomposition rate, and decomposition product of the carbon source gas. , further preferred is formazan, acetamethylene, ethylene, acetylene, propene, n-butene, isobutylene, 1,2-butadiene, 1,3-butadiene, cis-butadiene, anti-butadiene, positive As a carbon source gas of the present invention, any one or a combination of at least two of butyl sulfonium, isobutyl hydrazine, propylene, and propylene fluorene is preferable, and formazan is particularly preferable as the carbon source gas of the present invention.

在本发明中，衬底为金属箔或涂覆于基体上的金属薄膜。衬底的选择决定了石墨烯的生长温度、生长基质和使用的碳源气体的类型等，同时，金属的晶体类型和晶体取向也会影响石墨烯的生长质量。本发明在考虑了金属的熔点、溶碳量以及是否有稳定的金属碳化物等因素后，本发明所述衬底中的金属优选镍、铜、铷、钴、钯、铂、铱或钌中的任意 1种或至少 2种的组合，例如铜箔、镍箔、钯金属箔、覆盖有镍的薄膜、钴 -钯合金箔、铜 -铱-钌合金箔等，本发明所述衬底进一歩优选铜箔、镍箔、铷箔、钌箔或涂覆有金属镍薄膜的基体中的任意 1种或至少 2种的组合，进一歩优选铜箔、镍箔或覆有金属镍膜的基体中的任意 1种或至少 2种的组合，优选铜箔或覆有金属镍膜的基体。 In the present invention, the substrate is a metal foil or a metal thin film coated on the substrate. The choice of substrate determines the growth temperature of graphene, the growth matrix and the type of carbon source gas used. At the same time, the crystal type and crystal orientation of the metal also affect the growth quality of graphene. The present invention preferably optimizes the metal in the substrate of the present invention after considering factors such as the melting point of the metal, the amount of dissolved carbon, and whether there is a stable metal carbide or the like. Any one or a combination of at least two of nickel, copper, ruthenium, cobalt, palladium, platinum, rhodium or ruthenium, such as copper foil, nickel foil, palladium metal foil, nickel-coated film, cobalt-palladium alloy foil, a copper-bismuth-ruthenium alloy foil or the like, the substrate of the present invention is preferably any one or a combination of at least two of a copper foil, a nickel foil, a tantalum foil, a tantalum foil or a metal nickel film-coated substrate. Further, any one or a combination of at least two of a copper foil, a nickel foil or a metal nickel-coated substrate may be further preferably used, and a copper foil or a metal nickel-coated substrate is preferred.

作为优选技术方案，本发明所述化学气相沉积法制备单层或多层石墨烯的方法包括如下歩骤： As a preferred technical solution, the method for preparing a single layer or a plurality of graphene by the chemical vapor deposition method of the present invention comprises the following steps:

(1) 将衬底置于真空反应炉中； (1) placing the substrate in a vacuum reactor;

(2) 除去真空腔内的氧气； (2) removing oxygen from the vacuum chamber;

(3) 向真空腔内注入还原性气体； (3) injecting a reducing gas into the vacuum chamber;

(4) 升温； (4) heating up;

(5) 向真空腔内注入碳源气体，同时保持氢气流量； (5) injecting a carbon source gas into the vacuum chamber while maintaining a hydrogen flow rate;

(6) 降温，得沉积石墨烯的金属衬底； (6) cooling, a metal substrate on which graphene is deposited;

(7) 取出沉积有石墨烯的金属衬底。 (7) A metal substrate on which graphene is deposited is taken out.

优选地，本发明歩骤（2) 所述除去真空腔内的氧气包括如下歩骤： Preferably, the removing of oxygen in the vacuum chamber by the step (2) of the present invention comprises the following steps:

(2a) 将真空腔抽真空； (2a) evacuating the vacuum chamber;

(2b) 将惰性气体注入真空腔； (2b) injecting an inert gas into the vacuum chamber;

(2c) 将真空腔再次抽真空； (2c) vacuuming the vacuum chamber again;

(2d)重复歩骤（2b)和歩骤（2c)，直至将真空腔内的氧气分压 1x10— ⁶torr。优选地，歩骤 (2a) 抽真空至真空状态为 2-15x10— ²torr，例如 2xl0-²torr、 2.3 l0"²torr 2.7 l0"²torr 4.2 l0"²torr 4.9 l0"²torr 6.1 l0"²torr 6.7 l0"²torr 7.5x10— ²torr、 8.7x10— ²torr、 9x10— ²torr、 11.4x10— ²torr、 12.9x10— ²torr、 13.9x10— ²torr、 14.4x10— ²torr、 14.7 l0"²torr 15 l0"²torr等，进一歩优选 3-10 l0"²torr, 最优选 4-8x10— ²torr。 (2d) Repeat steps (2b) and (2c) until the oxygen in the vacuum chamber is divided by 1 x ^{10 - 6} torr. Preferably, the step (2a) is evacuated to a vacuum state of 2-15 x 10 - ² torr, for example 2xl0 - ² torr, 2.3 l0" ² torr 2.7 l0" ² torr 4.2 l0" ² torr 4.9 l0" ² torr 6.1 l0" ² torr 6.7 l0" ² torr 7.5x10 - ² torr, 8.7x10 - ² torr, 9x10 - ² torr, 11.4x10 - ² torr, 12.9x10 - ² torr, 13.9x10 - ² torr, 14.4x10 - ² torr, 14.7 l0 " ² torr 15 l0" ² torr, etc., further preferred 3-10 l0" ² torr, most preferred 4-8x10- ² torr.

优选地，歩骤（2b) 惰性气体的注入量为使真空腔内的压力为 ^lOtorr, 例如 lltorr、 18torr、 22torr、 34torr、 42torr、 57torr、 66torr、 70torr、 78torr、 80torr、 80.4torr、 85torr、 98torr、 99torr、 100torr、 101torr、 103.1torr、 163torr、 203torr、 255torr、 708torr、 1020torr等，进一歩优选 100torr。 Preferably, the inert gas is injected in the step (2b) such that the pressure in the vacuum chamber is ^10 Torr, for example, lltorr, 18torr, 22torr, 34torr, 42torr, 57torr, 66torr, 70torr, 78torr, 80torr, 80.4torr, 85torr, 98torr, 99torr, 100torr, 101torr, 103.1torr, 163torr, 203torr, 255torr, 708torr, 1020torr, etc., further preferably 100torr.

优选地，歩骤（2b) 所述惰性气体选自氮气、氦气、氖气、氩气、氪气、氙气中的任意 1种或至少 2种的组合，所述组合例如氮气 /氦气、氦气 /氖气、氩气 /氖气、氦气 /氪气 /氖气、氦气 /氖气 /氩气等。本发明对所述惰性气体的纯度不做具体限定，只需要将真空腔中的氧气除去以达到氧气分压 1x10— ⁶torr为标准即可，优选地，本发明所述的惰性气体的纯度为 99.99%。 Preferably, the inert gas of the step (2b) is selected from any one or a combination of at least two of nitrogen, helium, neon, argon, neon, xenon, such as nitrogen/helium, Helium/helium, argon/helium, helium/helium/helium, helium/helium/argon. The purity of the inert gas is not specifically limited in the present invention, and it is only required to remove oxygen in the vacuum chamber to achieve a partial pressure of oxygen of 1× ^{10 −6} torr. Preferably, the purity of the inert gas of the present invention is 99.99%.

优选地，歩骤 (2c) 抽真空至真空状态为 2-15x10— ²torr，例如 2xl0-²torr、 2.1x10— ²torr、 3.7x10— ²torr、 4.9x10— ²torr、 5.9x10— ²torr、 6.2x10— ²torr、 7.1x10— ²torr、 8.6x10— ²torr、 10.8x10— ²torr、 11x10— ²torr、 11.8x10— ²torr、 12.7x10— ²torr、 13.5x10— ²torr、 14.9xl0"²torr 14.3 l0"²torr 15 l0"²torr,优选 3-10xl0-²torr，最优选 4-8x10-²torr。 Preferably, the step (2c) is evacuated to a vacuum state of 2-15 x 10 - ² torr, for example 2xl0 - ² torr, 2.1x10 - ² torr, 3.7x10 - ² torr, 4.9x10 - ² torr, 5.9x10 - ² torr ^{^{, 6.2x10- 2 torr, 7.1x10- 2 torr}} , 8.6x10- 2 torr, 10.8x10- 2 torr, 11x10- 2 torr, 11.8x10- 2 torr, 12.7x10- 2 torr, 13.5x10- 2 torr, 14.9xl0 " ² torr 14.3 l0" ² torr 15 l0" ² torr, preferably 3-10xl0 - ² torr, most preferably 4-8x10 - ² torr.

优选地，歩骤（2d) 所述的歩骤（2b) 和歩骤（2c) 的重复次数为 2-8次，例如 2次、 3次、 4次、 6次、 8次，优选 2-5次，最优选 2-3次。 Preferably, the number of repetitions of the step (2b) and the step (2c) described in the step (2d) is 2-8 times, for example, 2 times, 3 times, 4 times, 6 times, 8 times, preferably 2- 5 times, most preferably 2-3 times.

歩骤（2)所述除去真空腔内的氧气的目的是为了防止经过化学气相沉积得到的石墨烯与真空腔中的气体发生反应，尤其是与其中的氧气发生反应。因此，歩骤（2)需要不断重复 "抽真空-充入惰性气体 -抽真空-充入惰性气体" 的歩骤，直至将真空腔内的氧气分压 1x10— ⁶torr，本领域技术人员应该明了，此处所述的氧气分压越低，最后得到的石墨烯的质量越好，例如所述的氧气分压为 l l0"⁶torr, 0.98 l0"⁶torr, 0.92 l0"⁶torr 0.82 l0"⁶torr 0.88xl()-⁶torr等。 The purpose of removing oxygen in the vacuum chamber as described in the step (2) is to prevent the graphene obtained by chemical vapor deposition from reacting with the gas in the vacuum chamber, especially with oxygen therein. Therefore, the step (2) requires repeated repetition of the steps of "vacuum-filling with inert gas-vacuum-filling with inert gas" until the partial pressure of oxygen in the vacuum chamber is 1 x ^{10 - 6} torr, which should be It is clear that the lower the partial pressure of oxygen described here, the better the quality of the finally obtained graphene, for example, the partial pressure of oxygen is l l0" ⁶ torr, 0.98 l0" ⁶ torr, 0.92 l0" ⁶ torr 0.82 l0 " ⁶ torr 0.88xl() - ⁶ torr and so on.

本发明中，气体的注入流量均独立的选自 1-lOOsccm，例如 l.lsccm、1.9sccm、 3.5sccm、 4.2sccm、 9.7sccm、 15sccm、 29sccm、 38sccm、 44sccm、 58.3sccm、 69sccm、 87sccm、 98sccm、 99.5sccm等，所述的气体的注入流量包括歩骤 (2) 所述的惰性气体流量、歩骤（3) 和歩骤（5) 所述的还原性气体（氢气）流量和歩骤（5) 所述的碳源气体流量以及歩骤（7) 所述的惰性气体流量等。 In the present invention, the injection flow rate of the gas is independently selected from 1-100 sccm, for example, l.lsccm, 1.9 sccm, 3.5 sccm, 4.2 sccm, 9.7 sccm, 15 sccm, 29 sccm, 38 sccm, 44 sccm, 58.3 sccm, 69 sccm, 87 sccm, 98 sccm, 99.5 sccm, etc., the injection flow rate of the gas includes the inert gas flow rate as described in the step (2), The reducing gas (hydrogen) flow rate as described in the steps (3) and (5), the carbon source gas flow rate as described in the step (5), and the inert gas flow rate as described in the step (7).

优选地，本发明所述的惰性气体的流量优选 4-96_SCCm，进一歩优选 20-80sccm; Preferably, the flow rate of the inert gas of the present invention is preferably 4-96 _SCC m, further preferably 20-80 sccm;

优选地，本发明所述还原性气体的流量优选 4-60sccm，进一歩优选 10-30sccm; Preferably, the flow rate of the reducing gas of the present invention is preferably 4-60 sccm, further preferably 10-30 sccm;

优选地，本发明所述碳源气体流量优选 l-40sccm，进一歩优选 l-10sccm。优选地，本发明所述还原性气体（氢气）的纯度 99.99%，例如 99.991%、 99.999%等。 Preferably, the carbon source gas flow rate of the present invention is preferably from 1 to 40 sccm, further preferably from 1 to 10 sccm. Preferably, the reducing gas (hydrogen) of the present invention has a purity of 99.99%, for example, 99.991%, 99.999%, and the like.

优选地，本发明所述碳源气体的纯度 99.99%，例如 99.991%、 99.999%等。歩骤（4) 所述升温的温度为石墨烯的生长温度，取决于衬底的种类和碳源的种类。优选地，本发明歩骤（4)所述升温的温度为 800-1150°C，例如 800°C、 801°C、 817°C、 832°C、 897°C、 922°C、 989°C、 1020 °C、 1090 °C、 1106°C、 1130 °C、 1170°C、 1200°C等，优选 800-1100°C，进一歩优选 880-1080°C，特别优选 950-1050。C。 Preferably, the carbon source gas of the present invention has a purity of 99.99%, for example, 99.991%, 99.999%, and the like. Step (4) The temperature of the temperature rise is the growth temperature of graphene, depending on the kind of the substrate and the kind of the carbon source. Preferably, the temperature of the temperature rise in the step (4) of the present invention is 800-1150 ° C, for example, 800 ° C, 801 ° C, 817 ° C, 832 ° C, 897 ° C, 922 ° C, 989 ° C 1020 ° C, 1090 ° C, 1106 ° C, 1130 ° C, 1170 ° C, 1200 ° C, etc., preferably 800-1100 ° C, further preferably 880-1080 ° C, particularly preferably 950-1050. C.

本发明歩骤（6)所述降温的速率决定了石墨烯沉积的速度和沉积得到的石墨烯的外观形貌，优选地，歩骤（6)所述降温为降至室温，降温速度为 2-18°C Is, 例如 2.1°C/s、 2.7°C/s、 5.8°C/s、 6.9°C/s、 7.6°C/s、 ll°C/s、 13.5°C/s、 16°C/s、 17.8°C/s等，优选 3-9°C/s，进一歩优选 8°C/s。 The rate of temperature drop as described in the step (6) of the present invention determines the rate of deposition of graphene and the appearance of the deposited graphene. Preferably, the temperature drop in step (6) is reduced to room temperature, and the rate of temperature drop is 2 -18 ° C Is, for example 2.1 ° C / s, 2.7 ° C / s, 5.8 ° C / s, 6.9 ° C / s, 7.6 ° C / s, ll ° C / s, 13.5 ° C / s, 16 ° C / s, 17.8 ° C / s, etc., preferably 3-9 ° C / s, further preferably 8 ° C / s.

本发明经过歩骤（1) - (6) 已经得到沉积于衬底的石墨烯，但是如果瞬间释放压力，大量的空气涌入真空腔，则肯定会造成石墨烯的氧化，如何将制得的石墨烯取出，并保证其不被空气中的氧气氧化，就需要进行歩骤（7 )，所述歩骤（7 ) 具体包括如下歩骤： The present invention has obtained graphene deposited on a substrate through steps (1) - (6), but if a moment of pressure is released, a large amount of air is poured into the vacuum chamber, which will definitely cause oxidation of graphene, how it will be produced. The graphene is taken out and ensured that it is not oxidized by oxygen in the air, and the step (7) is required. The step (7) specifically includes the following steps:

(7a) 关闭还原性气体进气阀、碳源气体进气阀和真空泵； (7a) closing the reducing gas intake valve, the carbon source gas intake valve, and the vacuum pump;

(7b) 打开惰性气体进气阀，充入惰性气体至真空腔内气压为 1个大气压； (7b) Open the inert gas inlet valve and fill with inert gas until the pressure in the vacuum chamber is 1 atmosphere;

(7c) 取出衬底。 (7c) Remove the substrate.

本发明通过采用化学气相沉积法，在金属衬底（铜箔或镍箔等）上高温裂解甲垸或其他碳源气体，沉积得到石墨烯薄膜，从而提供一种制备超大面积单层或者多层石墨烯薄膜的方法。 The present invention provides a method for preparing a super large-area single layer or a plurality of layers by pyrolyzing a formazan or other carbon source gas on a metal substrate (copper foil or nickel foil, etc.) by chemical vapor deposition. A method of graphene film.

能够达到以上发明目的的实验装置均可实现本发明，本领域技术人员可以根据自己掌握的专业知识实现在化学气相沉积制备单层和多层石墨烯的过程。本发明的优选技术方案是在真空反应炉中完成。本发明所述的真空反应炉为本领域技术人员所熟知的设备，典型但非限制性的有管式炉或气氛炉。 The present invention can be realized by an experimental apparatus capable of achieving the above object, and a person skilled in the art can realize a process of preparing a single layer and a plurality of layers of graphene by chemical vapor deposition according to his own expertise. A preferred embodiment of the invention is accomplished in a vacuum reactor. The vacuum reactor of the present invention is well known to those skilled in the art, and typically, but not exclusively, a tube furnace or an atmosphere furnace.

作为优选技术方案，本发明所述的化学气相沉积制备单层和多层石墨烯的方法在化学气相沉积***中进行，所述化学气相沉积***由惰性气体流量计 1、氢气流量计 2、碳源气体流量计 3、石英管 4、管式炉 5、真空计 6、衬底 7组成；其中，石英管 4置于管式炉 5中，石英管 4的一侧通过惰性气体流量计 1、氢气流量计 2、碳源气体流量计 3分别与惰性气体、氢气和碳源气体气瓶相连，石英管 4的另一侧依次与真空计 6和真空泵相连。 As a preferred technical solution, the method for preparing single-layer and multi-layer graphene by chemical vapor deposition according to the present invention is carried out in a chemical vapor deposition system, which comprises an inert gas flow meter, a hydrogen flow meter 2, and carbon. The source gas flow meter 3, the quartz tube 4, the tube furnace 5, the vacuum gauge 6, and the substrate 7 are composed; wherein, the quartz tube 4 is placed in the tube furnace 5, and one side of the quartz tube 4 passes through the inert gas flowmeter 1. The hydrogen flow meter 2 and the carbon source gas flow meter 3 are respectively connected to an inert gas, a hydrogen gas, and a carbon source gas cylinder, and the other side of the quartz tube 4 is sequentially connected to the vacuum gauge 6 and the vacuum pump.

作为另一个可选技术方案，所述的石英管和管式炉可以换成一个具有较大空间的气氛炉，其操作歩骤与上述管式炉相同。 As an alternative technical solution, the quartz tube and the tube furnace can be replaced by an atmosphere furnace having a larger space, and the operation step is the same as that of the above tube furnace.

作为可选技术方案，本发明所述化学气相沉积制备单层和多层石墨烯的方法包括如下歩骤： As an alternative technical solution, the method for preparing single-layer and multi-layer graphene by chemical vapor deposition according to the present invention comprises the following steps:

( 1 ) 将过渡金属衬底置于管式炉或气氛炉中； (2a) 将管式炉或气氛炉的气压抽真空至 4-8xl0—²torr_; (1) placing the transition metal substrate in a tube furnace or an atmosphere furnace; (2a) evacuating the air pressure of the tube furnace or the atmosphere furnace to 4-8xl0 to ² torr _;

(2b) 以气体流量 l-100sccm将纯度 99.99%的惰性气体注入到真空腔中； (2c) 关闭惰性气体进气阀门，将管式炉或气氛炉的气压抽至极限 4-8x10— ²torr; (2b) to the gas flow rate l-100sccm purity of 99.99% of an inert gas is injected into the vacuum chamber; (2C) close the inert gas inlet valve, the pressure tube furnace or a furnace atmosphere is evacuated to limit 4-8x10- ² torr ;

(2d) 重复操作歩骤（2b) 和歩骤（2c) 2〜3 次，直至将管式炉或气氛炉内的残余氧气除至氧气分压小于 lxl(T⁶torr_; (2d) Repeat step (2b) and step (2c) 2~3 times until the residual oxygen in the tube furnace or atmosphere furnace is removed to a partial pressure of oxygen less than lxl (T ⁶ torr _;

(3) 将氢气注入真空腔中； (3) injecting hydrogen into the vacuum chamber;

(4) 升温至 800-1100 °C; (4) Warming up to 800-1100 °C;

(5) 将碳源气体注入真空腔中，同时保持氢气流量； (5) injecting a carbon source gas into the vacuum chamber while maintaining a hydrogen flow rate;

(6) l-100mm后即得沉积石墨烯的金属衬底； (6) After l-100mm, the metal substrate of graphene is deposited;

(7b) 打开惰性气体进气阀，充入惰性气体至真空腔内气压为 1个大气压; (7c) 取出衬底。 (7b) Open the inert gas inlet valve and fill with inert gas until the pressure in the vacuum chamber is 1 atm; (7c) Remove the substrate.

可选地，本发明通过如下技术方案实现： Optionally, the present invention is implemented by the following technical solutions:

一种化学气相沉积制备单层和多层石墨烯的方法：将过渡金属衬底置于真空反应炉中，在除去真空腔内氧气的情况下，将氢气注入真空腔中，并升温至 800-1100 °C, 再将碳源气体注入真空腔中，同时保持氢气流量， l-100min后即得沉积石墨烯的金属衬底。 A method for preparing single-layer and multi-layer graphene by chemical vapor deposition: placing a transition metal substrate in a vacuum reactor, and injecting hydrogen into the vacuum chamber while removing oxygen in the vacuum chamber, and raising the temperature to 800- At 1100 °C, the carbon source gas is injected into the vacuum chamber while maintaining the hydrogen flow rate. After 1 to 100 minutes, the metal substrate of graphene is deposited.

优选地，所述除去真空腔内氧气的方法是： Preferably, the method for removing oxygen in the vacuum chamber is:

(1) 将管式炉或气氛炉的气压抽至极限真空状态 4-8X 10—²torr_; (1) A pressure tube furnace or a furnace atmosphere evacuated to ultimate vacuum 4-8X 10- ² _torr;

(2)以气体流量 l-100sccm将纯度高于 99.99%的惰性气体注入到真空腔中； (2) injecting an inert gas having a purity higher than 99.99% into the vacuum chamber at a gas flow rate of l-100 sccm;

(3) 关闭惰性气体进气阀门，将管式炉或气氛炉的气压抽至极限 4-8X 10"²torr_; (4) 重复操作歩骤（2) 和歩骤（3 ) 2-3 次，直至将管式炉或气氛炉内的残余氧气除至氧气分压小于 lX 10—⁶torr。 (3) Close the inert gas inlet valve and pump the air pressure of the tube furnace or the atmosphere furnace to the limit of 4-8X 10" ² torr _; (4) repeat step ho (2), and ho step (3) 2-3 times, until the atmosphere in the furnace or tube furnace residual oxygen in addition to the oxygen partial pressure is less than lX 10- ⁶ torr.

优选地，所述取出沉积石墨烯的金属衬底的方法是：关闭氢气和碳源气体阀门、真空泵，用惰性气体将管式炉或气氛炉气压充满到一个大气压状态，然后取出金属衬底。 Preferably, the method of extracting the metal substrate on which the graphene is deposited is: closing a hydrogen gas and a carbon source gas valve, a vacuum pump, filling the gas pressure of the tube furnace or the atmosphere furnace to an atmospheric pressure state with an inert gas, and then taking out the metal substrate.

优选地，所述氢气和碳源气体的流速为 l-100sccm，纯度高于 99. 99%。优选地，所述碳源气体为只含碳氢原子的有机气体。 The purity of the hydrogen gas and the carbon source gas is from 1 to 100 sccm, and the purity is higher than 99.99%. Preferably, the carbon source gas is an organic gas containing only hydrocarbon atoms.

优选地，所述碳源气体为甲垸。 Preferably, the carbon source gas is formazan.

优选地，所述金属衬底为铜箔、镍箔、铷箔或钌箔。 Preferably, the metal substrate is a copper foil, a nickel foil, a tantalum foil or a tantalum foil.

本发明的目的之二在于提供一种前述化学气相沉积的方法制备得到的石墨烯，所述石墨烯厚度可控；所述石墨烯的厚度为单原子层石墨烯或者多原子层石墨烯。本发明通过控制碳源气体和还原性气体的流速、升温温度、降温速率等操作条件，来得到单原子层石墨烯或者多原子层石墨烯。 A second object of the present invention is to provide a graphene prepared by the above method of chemical vapor deposition, wherein the thickness of the graphene is controllable; the thickness of the graphene is monoatomic layer graphene or polyatomic layer graphene. The present invention obtains a monoatomic layer graphene or a polyatomic layer graphene by controlling operating conditions such as a flow rate of a carbon source gas and a reducing gas, a temperature rising temperature, and a temperature decreasing rate.

优选地，所述石墨烯为多原子层石墨烯； Preferably, the graphene is a polyatomic layer graphene;

优选地，所述石墨烯为单原子层石墨烯。 Preferably, the graphene is a monoatomic layer graphene.

本发明的目的之三在于提供一种化学气相沉积制备单层和多层石墨烯的方法制备得到的石墨烯的用途，所述石墨烯用于能量储存活性材料、微处理器、电池、显示器和柔性电子器件，优选用于储氢、锂离子电池、超级电容器或者燃料电池，以及纳电子器件、高频电路、光子传感器、基因电子测序、减少噪音、高频 /射频晶体管、平板显示和柔性显示器。 A third object of the present invention is to provide a use of a graphene prepared by a method of chemical vapor deposition for preparing a single layer and a plurality of graphenes for use in an energy storage active material, a microprocessor, a battery, a display, and Flexible electronics, preferably for hydrogen storage, lithium-ion batteries, supercapacitors or fuel cells, as well as nanoelectronics, high frequency circuits, photon sensors, gene electronics sequencing, noise reduction, high frequency / RF transistors, flat panel displays and flexible displays .

与现有技术相比，本发明具有如下有益效果： Compared with the prior art, the present invention has the following beneficial effects:

( 1 ) 本发明提供的单层和多层石墨烯的化学气相沉积法的操作简单，操作条件易控，无需制备催化剂。 (2)本发明提供的单层和多层石墨烯的化学气相沉积法制备得到的石墨烯产品的尺寸（晶畴）可以达到厘米以上尺寸； (1) The chemical vapor deposition method of the single-layer and multi-layer graphene provided by the present invention is simple in operation, easy to control in operation conditions, and does not require preparation of a catalyst. (2) The size (crystal domain) of the graphene product prepared by the chemical vapor deposition method of the single layer and the multilayer graphene provided by the present invention can reach a size of more than a centimeter;

(3 )本发明提供的石墨烯产品缺陷峰低，具有极高晶体质量，透光性好（透射率优于 97%); (3) The graphene product provided by the invention has low defect peak, high crystal quality and good light transmittance (the transmittance is better than 97%);

(4) 本发明提供的石墨烯的厚度从单层到多层可控，容易得到单原子层石墨烯。 (4) The thickness of the graphene provided by the present invention is controllable from a single layer to a plurality of layers, and a monoatomic layer of graphene is easily obtained.

附图说明 DRAWINGS

附图用来提供对本发明的进一歩理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。 The drawings are intended to provide a further understanding of the invention, and are intended to be a part of the description of the invention.

图 1是本发明实施例 1-4所述化学气相沉积***的结构示意图； 1 is a schematic structural view of a chemical vapor deposition system according to Embodiments 1 to 4 of the present invention;

图 2是本发明实施例 3所制备石墨烯的拉曼光谱图。 Fig. 2 is a Raman spectrum diagram of graphene prepared in Example 3 of the present invention.

附图标记 Reference numeral

1-惰性气体流量计； 2-氢气流量计； 3-碳源气体流量计； 4-石英管； 5-管式炉； 6-真空计； 7-衬底。 1-inert gas flow meter; 2-hydrogen flow meter; 3-carbon source gas flow meter; 4-quartz tube; 5-tube furnace; 6-vacuum gauge;

具体实施方式 detailed description

为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。 In order to facilitate the understanding of the present invention, the present invention is exemplified by the following. It should be understood by those skilled in the art that the present invention is not to be construed as limited.

实施例 1 Example 1

通过化学气相沉积法在铜箔上制备石墨烯薄膜，所述方法在化学气相沉积 ***中进行，包括以下制备歩骤： A graphene film is prepared on a copper foil by chemical vapor deposition, and the method is carried out in a chemical vapor deposition system, including the following preparation steps:

( 1 ) 取 5cm长、 5cm宽、 25μπι厚铜箔衬底 7置于石英管 4中； (1) taking a 5 cm long, 5 cm wide, 25 μπ thick copper foil substrate 7 placed in the quartz tube 4;

(2a) 打开真空泵将石英管 4的气压抽至极限真空状态 4xl0—²torr_; (2a) to open the pressure of the quartz tube 4 to a vacuum pump evacuated to ultimate vacuum of 4xl0- ² _torr;

(2b) 惰性气体流量计 1设定为 5sccm，将氩气注入到真空腔中； (2c) 4.5min后，关闭惰性气体流量计 1 阀门，将管式炉 5的气压抽至极限 8xl0-²to (2b) The inert gas flow meter 1 is set to 5 sccm, and argon gas is injected into the vacuum chamber; After (2c) 4.5min, an inert gas flow to close the valve 1, the tube furnace evacuated to a pressure of 5 8xl0- ² to limit

(2d) 重复歩骤（2b) 和歩骤（2c) 的操作歩骤 3次；直到将石英管 4的残余氧气驱赶干净至氧气分压小于 lxl(T⁶torr_; (2d) Repeat the steps of step (2b) and step (2c) three times; until the residual oxygen of quartz tube 4 is driven clean until the partial pressure of oxygen is less than lxl (T ⁶ torr _;

(3) 氢气流量计 2设定为 5sccm，将氢气注入到真空腔中； (3) The hydrogen flow meter 2 is set to 5sccm, and hydrogen gas is injected into the vacuum chamber;

(4) 将管式炉 5的温度升高到 1000°C_; (4) Raise the temperature of the tube furnace 5 to 1000 ° C _;

(5) 碳源气体流量计 3设定 5sccm，将甲垸注入到真空腔中； (5) Carbon source gas flow meter 3 Set 5sccm, inject the nail into the vacuum chamber;

(6) 将管式炉 5的温度降至室温，降温速度为 15°C/s; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 15 ° C / s;

(7a) 关闭氢气流量计 2、碳源气体流量计 3阀门以及真空泵； (7a) Close the hydrogen flow meter 2. Carbon source gas flow meter 3 valve and vacuum pump;

(7b) 惰性气体流量计 1设定为 50sccm，用氩气将石英管 4气压充满到一个大气压状态； (7b) The inert gas flow meter 1 is set to 50 sccm, and the quartz tube 4 gas pressure is filled with argon gas to an atmospheric pressure state;

(7c)打开石英管 4真空接口，取出己沉积石墨烯的铜箔衬底 7。所制备石墨烯尺寸为 5x5cm²。 (7c) The quartz tube 4 vacuum port was opened, and the copper foil substrate 7 on which the graphene was deposited was taken out. The graphene prepared had a size of 5 x ⁵ cm ² .

实施例 2 Example 2

通过化学气相沉积法在镍膜上制备石墨烯薄膜，所述方法在化学气相沉积 ***中进行，包括以下制备歩骤： A graphene film is prepared on a nickel film by a chemical vapor deposition method, which is carried out in a chemical vapor deposition system, and includes the following preparation steps:

(1) 通过磁控溅射在 5x5cm²硅衬底 7上蒸镀 500nm厚度镍膜；取蒸镀好镍膜的硅衬底 7置于石英管 4中； (1) depositing a 500 nm thick nickel film on a 5× ⁵ cm ² silicon substrate 7 by magnetron sputtering; taking a silicon substrate 7 on which a nickel film is deposited is placed in the quartz tube 4;

(2a) 打开真空泵将石英管 4的气压抽至极限真空状态 8χ10—² torn (2a) Open the vacuum pump to pump the air pressure of the quartz tube 4 to the ultimate vacuum state 8χ10 — ² torn

(2b) 惰性气体流量计 1设定为 50sccm，将氦气注入到真空腔中； (2b) Inert gas flow meter 1 is set to 50sccm, and helium gas is injected into the vacuum chamber;

(2c) 4.5分钟后，关闭惰性气体流量计 1阀门，将管式炉 5的气压抽至极限 4xlO-²to (2c) After 4.5 minutes, close the inert gas flow meter 1 valve and pump the air pressure of the tube furnace 5 to the limit of 4xlO- ² to

(2d) 重复歩骤（2b) 和歩骤（2c) 的操作歩骤 2次；直到将石英管 4的残余氧气驱赶干净至氧气分压小于 lxl(T⁶torr_; (2d) repeat the steps of step (2b) and step (2c) twice; until the quartz tube 4 Residual oxygen is driven clean until the partial pressure of oxygen is less than lxl (T ⁶ torr _;

(3) 氢气流量计 2设定为 50sccm，将氢气注入到真空腔中； (3) The hydrogen flow meter 2 is set to 50sccm, and hydrogen gas is injected into the vacuum chamber;

(4) 将管式炉 5的温度升高到 900 °C_; (4) Raise the temperature of the tube furnace 5 to 900 °C _;

(5) 碳源气体流量计 3设定 50sccm，将乙垸注入到真空腔中； (5) Carbon source gas flow meter 3 Set 50sccm, inject the acetonitrile into the vacuum chamber;

(6) 将管式炉 5的温度降至室温，降温速度为 13°C/s; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 13 ° C / s;

(7b)惰性气体流量计 1设定为 lOOsccm, 用氦气将石英管 4气压充满到一个大气压状态； (7b) The inert gas flow meter 1 is set to lOOsccm, and the quartz tube 4 is filled with helium gas to an atmospheric pressure state;

(7c)打开石英管 4真空接口，取出己沉积石墨烯的镍膜衬底 7。所制备石墨烯尺寸为 5x5cm²。 (7c) The quartz tube 4 vacuum port was opened, and the nickel film substrate 7 on which graphene was deposited was taken out. The graphene prepared had a size of 5 x ⁵ cm ² .

实施例 3 Example 3

(2a) 打开真空泵将石英管 4的气压抽至极限真空状态 6xl0—²torr_; (2a) to open the pressure of the quartz tube 4 to a vacuum pump evacuated to ultimate vacuum of 6xl0- ² _torr;

(2b) 惰性气体流量计 1设定为 lOOsccm, 将氮气注入到真空腔中； (2b) Inert gas flow meter 1 is set to lOOsccm, and nitrogen gas is injected into the vacuum chamber;

(2c) 4.5分钟后，关闭惰性气体流量计 1阀门，将管式炉 5的气压抽至极限 6xl0-²to (2c) 4.5 minutes later, the inert gas flow to close the valve 1, the tube furnace evacuated to a pressure of 5 6xl0- ² to limit

(2d) 重复歩骤（2b) 和歩骤（2c) 的操作歩骤 2次；直到将石英管 4的残余氧气驱赶干净至氧气分压小于 lxl(T⁶torr_; (2d) Repeat the operation of step (2b) and step (2c) twice; until the residual oxygen of quartz tube 4 is driven clean until the partial pressure of oxygen is less than lxl (T ⁶ torr _;

(3) 氢气流量计 2设定为 lOOsccm, 将氢气注入到真空腔中； (3) The hydrogen flow meter 2 is set to lOOsccm, and hydrogen gas is injected into the vacuum chamber;

(4) 将管式炉 5的温度升高到 800 °C_; ( 5 ) 碳源气体流量计 3设定 lOOsccm, 将乙烯注入到真空腔中；(4) Raise the temperature of the tube furnace 5 to 800 °C _; (5) The carbon source gas flow meter 3 is set to 100 sccm, and ethylene is injected into the vacuum chamber;

(6) 将管式炉 5的温度降至室温，降温速度为 5°C/s_; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 5 ° C / s _;

(7b) 惰性气体流量计 1设定为 75sccm，用氮气将石英管 4气压充满到一个大气压状态； (7b) The inert gas flow meter 1 is set to 75 sccm, and the quartz tube 4 is filled with nitrogen gas to an atmospheric pressure state;

(7c)打开石英管 4真空接口，取出已沉积石墨烯的镍膜衬底 7。所制备石墨烯尺寸为 5x5cm²。 (7c) The quartz tube 4 vacuum port is opened, and the nickel film substrate 7 on which graphene has been deposited is taken out. The graphene prepared had a size of 5 x ⁵ cm ² .

图 2是实施例 3所得石墨烯的拉曼光谱，从该图可以看出： Figure 2 is a Raman spectrum of graphene obtained in Example 3, from which it can be seen that:

( 1 ) 存在石墨烯的两个本征拉曼峰 -G峰和 2D峰（1580cm— ¹和 2680cm—¹ ) ;(1) There are two intrinsic Raman-G peaks and 2D peaks of graphene (1580 cm- ¹ and 2680 cm- ¹ );

(2) 2D峰的强度大约为 G峰的两倍，说明所得石墨烯为单原子层；(2) The intensity of the 2D peak is about twice that of the G peak, indicating that the obtained graphene is a monoatomic layer;

(3 )缺陷峰 -D峰（1350cm—¹ ) 几乎不能分辨，说明所得石墨烯具有极高晶体质量。 (3) The defect peak-D peak (1350 cm- ¹ ) is almost indistinguishable, indicating that the obtained graphene has extremely high crystal quality.

实施例 4 Example 4

( 1 ) 取 5x5cm²见方、 20μπι厚的铜-钯合金箔衬底置于真空反应炉中；(1) taking a 5x5 cm ² square, 20 μπ thick copper-palladium alloy foil substrate in a vacuum reactor;

(2a) 打开真空泵将石英管 4的气压抽至极限真空状态 2x l0—²torr_; (2a) Open the vacuum pump to pump the air pressure of the quartz tube 4 to the ultimate vacuum state 2x l0 - ² torr _;

(2c) 7min后，关闭惰性气体流量计 1阀门，将管式炉 5的气压抽至极限 (2c) After 7 minutes, close the inert gas flow meter 1 valve and draw the air pressure of the tube furnace 5 to the limit.

15 l0"²torr: 15 l0" ² torr:

(2d) 重复歩骤（2b) 和歩骤（2c) 的操作歩骤 8次；直到将石英管 4的残余氧气驱赶干净至氧气分压小于 0.89x l0—⁶torr_; (2d) ho repeating step (2b) and ho step (2c) of the operation of step 8 ho; until the residual oxygen in the quartz tube 4 is driven to clean and oxygen partial pressure of less than 0.89x l0- ⁶ _torr;

(3 ) 氢气流量计 2设定为 lsccm, 将氢气注入到真空腔中； (4) 将管式炉 5的温度升高到 1150°C _; (3) The hydrogen flow meter 2 is set to lsccm, and hydrogen gas is injected into the vacuum chamber; (4) Raise the temperature of the tube furnace 5 to 1150 ° C _;

( 5 ) 碳源气体流量计 3设定 1.5sccm，将顺 1,3-丁二烯注入到真空腔中； (5) The carbon source gas flow meter 3 is set to 1.5 sccm, and cis 1,3-butadiene is injected into the vacuum chamber;

(6) 将管式炉 5的温度降至室温，降温速度为 2°C/s_; (6) The temperature of the tube furnace 5 is lowered to room temperature, and the cooling rate is 2 ° C / s _;

(7b) 惰性气体流量计 1设定为 80sccm，用氦气将石英管 4气压充满到一个大气压状态； (7b) The inert gas flow meter 1 is set to 80sccm, and the quartz tube 4 is filled with helium gas to an atmospheric pressure state;

申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。 The Applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims

WO 2012/167701 权利要求书 PCT/CN2012/076194 WO 2012/167701 Claim PCT/CN2012/076194

1、一种化学气相沉积制备单层和多层石墨烯的方法，其特征在于，所述方法是在还原气氛中，将碳源气体通过从高温逐渐降温的方式沉积在衬底上，从而得到单层和 /或多层石墨烯；所述还原气氛为氢气气氛。 A method for preparing single-layer and multi-layer graphene by chemical vapor deposition, characterized in that the method is to deposit a carbon source gas on a substrate by gradually decreasing the temperature from a high temperature in a reducing atmosphere, thereby obtaining Single layer and/or multilayer graphene; the reducing atmosphere is a hydrogen atmosphere.

2、如权利要求 1所述的方法，其特征在于，所述碳源气体为只含有碳原子和氢原子的有机气体，优选 C1-C4的垸烃、 C2-C4的烯烃、 C2-C3的炔烃中的任意 1种或至少 2种的组合，进一歩优选甲垸、乙垸、乙烯、乙炔、丙垸、正丁烯、异丁烯、 1,2-丁二烯、 1， 3-丁二烯、顺丁二烯、反二丁烯、正丁垸、异丁垸、丙烯、环丙垸中的任意 1种或至少 2种的组合，特别优选甲垸。 2. The method according to claim 1, wherein the carbon source gas is an organic gas containing only carbon atoms and hydrogen atoms, preferably a C1-C4 anthracene hydrocarbon, a C2-C4 olefin, a C2-C3 Any one or a combination of at least two of the alkyne, preferably a formazan, acetamethylene, ethylene, acetylene, propylene, n-butene, isobutylene, 1,2-butadiene, 1, 3-butadiene Any combination of at least one of olefin, butadiene, trans-dibutene, n-butylene, isobutyl hydrazine, propylene, and propylene fluorene is particularly preferably a formazan.

3、如权利要求 1或 2所述的方法，其特征在于，所述衬底选自金属箔或附于基体上的金属薄膜，所述金属选自镍、铜、铷、钴、钯、铂、铱或钌中的任意 1种或至少 2种的组合，优选铜箔、镍箔、铷箔、钌箔或涂覆有金属镍薄膜的基体中的任意 1种或至少 2种的组合，进一歩优选铜箔、镍箔或覆有金属镍膜的基体中的任意 1种或至少 2种的组合，优选铜箔或覆有金属镍膜的基体。 3. The method according to claim 1 or 2, wherein the substrate is selected from the group consisting of a metal foil or a metal film attached to the substrate, the metal being selected from the group consisting of nickel, copper, ruthenium, cobalt, palladium, platinum Any one or a combination of at least two of 铱, 铱 or ,, preferably any one or a combination of at least two of copper foil, nickel foil, ruthenium foil, ruthenium foil or metal nickel film-coated substrate. A combination of any one or at least two of a copper foil, a nickel foil or a metal nickel-coated substrate is preferably a copper foil or a metal nickel-coated substrate.

4、如权利要求 1-3之一所述的方法，其特征在于，所述方法包括如下歩骤： 4. Method according to one of claims 1-3, characterized in that the method comprises the following steps:

( 1 ) 将衬底置于真空反应炉中； (1) placing the substrate in a vacuum reactor;

(2) 除去真空腔内的氧气； (2) removing oxygen from the vacuum chamber;

(3 ) 向真空腔内注入还原性气体； (3) injecting a reducing gas into the vacuum chamber;

(4) 升温； (4) heating up;

(5) 向真空腔内注入碳源气体，同时保持还原性气体流量； (5) injecting a carbon source gas into the vacuum chamber while maintaining a reducing gas flow rate;

5、如权利要求 4所述的方法，其特征在于，歩骤（2) 所述除去真空腔内的氧气包括如下歩骤：（2a)将真空腔抽真空；（2b)将惰性气体注入真空腔； (2c) 将真空腔再次抽真空；（2d) 重复歩骤（2b) 和歩骤（2c)，直至将真空腔内的氧气分压 lxl0-⁶torr_; 5. The method according to claim 4, wherein the removing the oxygen in the vacuum chamber by the step (2) comprises the steps of: (2a) vacuuming the vacuum chamber; (2b) injecting the inert gas into the vacuum Cavity; (2c) The vacuum chamber is evacuated again; (2D) ho repeating step (2b) and ho step (2c), the vacuum chamber until the oxygen partial pressure lxl0- ⁶ _torr;

优选地，歩骤（2a)抽真空至真空状态为 2-15xl0—²torr，优选 3-10xl0—²torr，最优选 4-8xl0-²torr; Preferably, the step (2a) is evacuated to a vacuum of 2-15 x 10 - ² torr, preferably 3 - 10 x 10 - ² torr, and most preferably 4 - 8 x 10 - ² torr;

优选地，歩骤（2b) 惰性气体的注入量为使真空腔内的压力为 ^lOtorr, 优选 100 11~_; 优选地，歩骤（2b) 所述惰性气体选自氮气、氦气、氖气、氩气、氪气、氙气中的任意 1种或至少 2种的组合； Preferably, the inert gas is injected in the vacuum chamber so that the pressure in the vacuum chamber is 10 Torr, preferably 100 11 〜 _; preferably, the inert gas is selected from the group consisting of nitrogen, helium and neon. Any one or a combination of at least two of argon, helium and neon;

优选地，歩骤（2c)抽真空至真空状态为 2-15xl0—²torr，优选 3-10xl0—²torr，最优选 4-8xl0-²torr; Preferably, the step (2c) is evacuated to a vacuum of 2-15 x 10 - ² torr, preferably 3 - 10 x 10 - ² torr, and most preferably 4 - 8 x 10 - ² torr;

优选地，歩骤（2d) 所述的歩骤（2b) 和歩骤（2c) 的重复次数为 2-8次，优选 2-5次，最优选 2-3次。 Preferably, the number of repetitions of the step (2b) and the step (2c) described in the step (2d) is 2-8 times, preferably 2-5 times, and most preferably 2-3 times.

6、如权利要求 4或 5所述的方法，其特征在于，歩骤（4) 所述升温的温度为 800-1150 °C,优选 800-1100。C，进一歩优选 880-1080°C，特别优选 950-1050 °C; The method according to claim 4 or 5, characterized in that the temperature of the temperature rising in the step (4) is 800 to 1150 ° C, preferably 800 to 1100. C, further preferably 880-1080 ° C, particularly preferably 950-1050 ° C;

优选地，歩骤（3) 和歩骤（5) 所述的还原性气体和碳源气体的注入流量独立地限定为 1-lOOsccm; 所述还原性气体流量，进一歩优选 4-60sccm，特别优选 10-30sccm; 所述碳源气体流量，进一歩优选 l-40sccm，特别优选 1-lOsccm; 优选地，所述还原性气体和碳源气体的纯度独立地限定为 99.99%；优选地，歩骤（6) 所述降温为降至室温，降温速度为 2-18°C/s，优选 3-9 °C/s，进一歩优选 8°C/s。 Preferably, the injection flow rates of the reducing gas and the carbon source gas described in the steps (3) and (5) are independently defined as 1-100 sccm; and the reducing gas flow rate is further preferably 4-60 sccm, particularly Preferably, the flow rate of the carbon source gas is further preferably from 1 to 40 sccm, particularly preferably from 1 to 10 sccm; preferably, the purity of the reducing gas and the carbon source gas is independently defined as 99.99%; preferably, 歩The temperature drop in step (6) is to fall to room temperature, and the temperature drop rate is 2-18 ° C / s, preferably 3-9 ° C / s, further preferably 8 ° C / s.

7、如权利要求 4-6之一所述的方法，其特征在于，歩骤（7)所述取出沉积有石墨烯的金属衬底包括如下歩骤： 7. The method according to any one of claims 4-6, wherein the extracting the metal substrate deposited with graphene as described in step (7) comprises the following steps:

(7a) 关闭还原性气体进气阀、碳源气体进气阀和真空泵； (7b) 打开惰性气体进气阀，充入惰性气体至真空腔内气压为 1个大气压； (7c) 取出衬底。 (7a) closing the reducing gas intake valve, the carbon source gas intake valve, and the vacuum pump; (7b) Open the inert gas inlet valve and fill with inert gas until the pressure in the vacuum chamber is 1 atm; (7c) Remove the substrate.

8、如权利要求 1-7之一所述的方法，其特征在于，所述方法包括如下歩骤： ( 1 ) 将过渡金属衬底置于管式炉或气氛炉中； The method according to any one of claims 1 to 7, wherein the method comprises the following steps: (1) placing the transition metal substrate in a tube furnace or an atmosphere furnace;

(2a) 将管式炉或气氛炉的气压抽真空至 4-8x l0—²torr_; (2a) evacuating the air pressure of the tube furnace or the atmosphere furnace to 4-8x l0 to ² torr _;

(2b) 以气体流量 l-100sccm将纯度高于 99.99%的惰性气体注入到真空腔中； (2b) injecting an inert gas having a purity higher than 99.99% into the vacuum chamber at a gas flow rate of l-100 sccm;

( 2c ) 关闭惰性气体进气阀门，将管式炉或气氛炉的气压抽至极限 4-8x 10— ²torr; (2c) closing the inert gas inlet valve, pumping the pressure of the tube furnace or the atmosphere furnace to the limit of 4-8x 10 - ² torr;

(2d) 重复操作歩骤（2b) 和歩骤（2c) 2-3次，直至将管式炉或气氛炉内的残余氧气除至氧气分压小于 l x l(T⁶torr_; (2d) Repeat operation of step (2b) and step (2c) 2-3 times until the residual oxygen in the tube furnace or atmosphere furnace is removed to a partial pressure of oxygen of less than lxl (T ⁶ torr _;

(3 ) 将氢气注入真空腔中； (3) injecting hydrogen into the vacuum chamber;

(4) 升温至 800-1100 °C ; (4) Warming up to 800-1100 °C;

( 5 ) 将碳源气体注入真空腔中，同时保持氢气流量； (5) injecting a carbon source gas into the vacuum chamber while maintaining a hydrogen flow rate;

(7c) 取出衬底。 (7c) Remove the substrate.

9、一种如权利要求 1-8之一所述的化学气相沉积的方法制备得到的石墨烯，其特征在于，所述石墨烯厚度可控； A graphene prepared by the method of chemical vapor deposition according to any one of claims 1-8, wherein the graphene has a thickness that is controllable;

10、一种如权利要求 9所述的化学气相沉积的方法制备得到的石墨烯的用途，其特征在于，所述石墨烯用于能量储存活性材料、微处理器、电池、显示器和柔性电子器件，优选用于储氢、锂离子电池、超级电容器或者燃料电池，以及纳电子器件、高频电路、光子传感器、基因电子测序、减少噪音、高频 /射频晶体管、平板显示和柔性显示器。 10. A graphene prepared by the method of chemical vapor deposition according to claim 9 The graphene is used for energy storage active materials, microprocessors, batteries, displays, and flexible electronic devices, preferably for hydrogen storage, lithium ion batteries, supercapacitors or fuel cells, and nanoelectronic devices, High frequency circuits, photon sensors, gene electronics sequencing, noise reduction, HF/RF transistors, flat panel displays and flexible displays.