IntechOpen

Home > Books > Chemical Vapor Deposition for Nanotechnology

Open access peer-reviewed chapter

Large-Area Synthesis and Growth Mechanism of Graphene by Chemical Vapor Deposition

Written By

Chen Wang, Kizhanipuram Vinodgopal and Gui-Ping Dai

Submitted: 22 February 2018 Reviewed: 05 July 2018 Published: 05 November 2018

DOI: 10.5772/intechopen.79959

Chemical Vapor Deposition for Nanotechnology IntechOpen
Chemical Vapor Deposition for Nanotechnology Edited by Pietro Mandracci

From the Edited Volume

Chemical Vapor Deposition for Nanotechnology

Edited by Pietro Mandracci

Book Details Order Print

Chapter metrics overview

2,627 Chapter Downloads

View Full Metrics
Advertisement

Abstract

There has been continuous progress in the development of different synthesis methods to readily produce graphene at a lower cost. Compared with the other methods, chemical vapor deposition (CVD) is an effective and powerful method of producing graphene and has attracted increased attention during the last decade. In this way, we can obtain good uniformity with a multitude of domains, excellent quality, and large scale of the produced graphene. Meanwhile, it is also helping for large-area synthesis of single-crystal graphene. In the CVD method, precursors are typically absorbed on the surface followed by pyrolytic decomposition, which leads to the generation of absorption sites on the surface and promotes the growth of continuous thin films.

Keywords

  • chemical vapor deposition
  • graphene
  • large-scale synthesis
  • growth mechanism

1. Introduction

Graphene (shown in Figure 1), as a versatile two-dimensional material [1], has attracted great interest in the research community owing to its high mechanical stiffness [2], great flexibility [3], and stable chemical properties [4, 5, 6]. Based on the properties of graphene and its nano-scale thickness, it has been selected as a material for various applications in electrical, chemical, mechanical, optical, and catalysis industries [7, 8, 9, 10, 11]. Hence, it is very critical to propose methods for preparing high-quality graphene film.

Figure 1.

The schematic diagram of graphene.

Compared with other methods, such as mechanical exfoliation of graphite [12, 13, 14], liquid-phase exfoliation [15, 16], and reduction of graphene oxide (GO) [17, 18], chemical vapor deposition (CVD) is regarded as the most promising way for large-scale graphene production at a large scale with low defects, good uniformity, and controlled number of graphene layers, which has attracted intense research attention during the last decades [19, 20, 21, 22]. CVD involves the activation of gaseous reactants and the subsequent chemical reaction, followed by the formation of a stable solid deposit over a suitable substrate such as Ni [6, 23], Cu [5, 24, 25], Fe [26], Pt [27, 28], or their alloys [29, 30]. As early as 1969, Robertson et al. [31] discovered that chemical vapor deposition in the presence of methane produces a layer of graphite on some transition metal surfaces. However, even if the prepared graphene displays excellent performance, it cannot be applied to the related devices due to the limitations of deposition on the metal surface. The advent of poly(methyl methacrylate)-mediated nanotransfer printing technology [32] enabled the successful transfer of graphene from the growth substrate to any other substrate, and it also completely changed the status of chemical vapor deposition methods in the preparation method of graphene.

It is worth mentioning that, compared to exfoliated graphene obtained from natural graphite, the CVD graphene still shows a lower carrier mobility ranging from 100 to 1000 cm2/(V⋅s), due to the presence of growth defects and boundaries [33]. Therefore, a feasible route to improve graphene film quality lies in increasing the domain size that enables to avoid the side effect of graphene domain boundaries.

Now, large-area graphene synthesized have generally been single crystalline, and related research is aimed to control the domain size, defects, number of graphene layers, and so on. With regard to desired graphene, there are many effect parameters including hydrogen, oxygen, gas flow rate, and residence time.

In addition, great success has been achieved in the fabrication of large-area, single-crystalline graphene. Different teams have published reports on the single crystals. We also summarize these experimental results.

There are already many comprehensive articles published about increasing the size of graphene. Among these articles, a publication by Xu et al. [34] reports the fabrication of meter-size single-crystal graphene. The authors developed an innovative method to achieve the ultrafast epitaxial growth of meter-sized single-crystal graphene on a commercially available Cu foil (shown in Figure 2).

Figure 2.

Image of meter-size single-crystal graphene. Reproduced with permission of ref. [34].

In this chapter, we talk about the preparation of high-quality graphene in recent years, effect of experimental parameters, challenges of preparation of high-quality graphene, and timeline of graphene production. Finally, development trend and application prospect of CVD graphene are described.

Advertisement

2. Preparation of graphene

Great effort has been given to the synthesis of graphene with controlled size, morphology, edge structures, and layer numbers [22, 35, 36, 37, 38, 39, 40]. Studies into the dynamics of CVD graphene growth on copper foils have chiefly focused on monolayer films that develop under vacuum conditions. Up to now, the preparation methods of graphene are usually divided into two ways: physical and chemical (shown in Figure 3). With respect to physical method, mechanical exfoliation [12, 13, 14] and liquid-phase exfoliation [15, 16] are always used. With respect to chemical methods, they include CVD, reduction of graphene oxide (GO) [17, 18], epitaxial growth on various substrates.

Figure 3.

Classification of graphene synthesis techniques.

2.1. Mechanical exfoliation

The mechanical exfoliation method can provide the highest quality graphene sheets, which strips the graphene layers from the surface of graphite crystals by mechanical force. It is not suitable for mass production, however, because of the difficulty in controlling the number of layers and the size of sheets.

2.2. Liquid-phase exfoliation

Liquid-phase exfoliation cannot produce graphene films with high electronic quality, where scatter graphite to specific solvents or surfactants, and strip the single layer or multilayer graphene through ultrasonic energy to get graphene dispersions [15, 41].

2.3. Reduced graphene oxide (RGO)

With regard to RGO methods, first, the graphite is oxidized by treatment with KMnO4, NaNO3, and so on. Second, GO prepared from flake graphite can be readily dispersed in water and has been used on a large scale for preparing large graphitic films, but it would result defects in graphene [42].

2.4. Chemical vapor deposition

In comparison, CVD is an effective and powerful method of producing graphene. CVD processes typically involve two steps: the activation of gaseous reactants and the chemical reaction of forming a stable solid deposit over a suitable substrate [43, 44]. The deposition process consists of two types of reactions: homogeneous gas-phase reactions, occurring in the gas phase, and heterogeneous chemical reactions that occur on a heated surface. Therefore, CVD method is the use of carbon source (gas, liquid, and solid) decomposing in the high-temperature reaction zone, the release of carbon atoms in the metal substrate, eventually it forms a continuous graphene membrane. And many researchers use CVD method to prepare the high-quality and large-area graphene, as Li et al. [45] pointed (shown in Figure 4). Subsequently, CVD can be divided into two types: (I) thermal CVD and (II) plasma-enhanced CVD.

Figure 4.

Schematic diagram of growth mechanism of graphene on the metal substrate. Reproduced with permission of ref. [45].

2.5. Epitaxial growth on substrates

Obviously, the term “epitaxial growth” means ordered or arranged atomic growth in single crystalline manner over a single-crystalline substrate. When the substrate deposited materials are the same as the substrate, it is called homoepitaxial growth. Oppositely, it is defined as hetero epitaxial growth if substrate differs from the deposited materials. And epitaxial growth of graphite on semiconducting substrates (SiC) was known to us since 1975 [46]. Berger’s group successfully synthesized epitaxial graphene sheet [47] by using Si terminated face of single-crystal 6H-SiC by thermal desorption of Si. To summarize, although it is still an expensive approach, this is a promising method and possibly be scalable commercially.

Advertisement

3. CVD synthesis mechanism and the choice of carbon source

Chemical vapor deposition has been used to prepare inorganic materials in recent years. Besides, it also can be applied to produce graphene. CVD is the process of using gaseous matter to react on a solid surface and form solid deposits. The thermal decomposition and thermal synthesis of the deposition techniques are carried out at high temperature. As for the synthesis of graphene, three steps are generally required:

  1. a volatile precursor,

  2. transport of volatile matter to the precipitation area, and

  3. chemical reaction on the substrate to produce a solid substance.

Two phenomenological growth mechanisms have been proposed based on an isotope labeling experiments [12] to understand the graphene growth. It is very easy to form a metal-carbide phase due to the strong interaction between carbon and metal [45, 48, 49, 50], following the precipitated growth mechanism. During the subsequent cooling process, the pyrolytic carbon atoms from the carbon sources firstly dissolve into the catalyst and then deposit at the metal surface to form graphene layers. On the other hand, the pyrolytic carbon atoms could only diffuse on the catalyst surface as the cases are shown with Cu and Au when the interaction between metal and carbon is fairly weak [22, 51], where both the nucleation and growth of graphene are dominated by the surface diffusion of the decomposed carbon atoms. Multi-layered graphene film formation normally follows the sedimentary growth mechanism and the number of graphene layers can be controlled by adjusting the dissolved C atoms in the metals or the thickness and composition of the substrate or by slowing down the cooling rate. Obviously, only single-layer graphene can be formed in the diffusive growth because the feedstock cannot get access to the graphene covered area of catalyst surface.

Meantime, SLG (shown in Figure 5) has been synthesized from solid and liquid hydrocarbon sources at different temperature (400–1000°C). Li et al. [52] adopted polymethyl-methacrylate (PMMA) and polystyrene as solid hydrocarbon and benzene as a liquid hydrocarbon source to grow graphene at temperatures lower than 1000°C on copper foil. Jang et al. [53] tried to remove remaining oxidizing impurities (oxygen-free APCVD, which is shown in Figure 6) before graphene deposition by using pumping and purging. This method leads to continuous SLG with full coverage of the substrate.

As for the multilayer graphene (MLG), the high solubility of carbon in catalysts results in the dissolution of carbon into the bulk at high temperatures, leading to multilayer graphene (MLG) during the cooling process [33, 54, 55, 56].

Advertisement

4. Toward high-quality graphene: effect of experimental parameters

4.1. Choice of metal base material

Up to now, a large number of research have been done about the growth of graphene on the metal surfaces. CVD graphene growth is strongly dependent on the catalyst. Due to the different catalytic activity and atomic packing, the growth behavior of graphene on catalyst surfaces, such as quality, continuity, and layer number, is different in each case. The catalyst plays an important role in the CVD process. We generally use Cu [5, 24, 25], Ni [6, 23], Pd [49], Ru [57], and Ir [58], as the metal base material for the preparation of graphene. As we know, different metal base materials have a different effect on the preparation of graphene, so the metal substrate is the key factor to determine the growth of graphene.

The mechanism of growth of graphene by chemical vapor deposition in copper and nickel substrate is different. Studies have shown that the growth of graphene on other metal substrates can also be basically classified into the growth mechanisms of copper and nickel substrates. On a metal substrate with high soluble carbon content, such as nickel, the carbon atoms produced by the carbon source cracking are infiltrated into the metal matrix at high temperature. When the temperature drops, the core is precipitated from the inside, then the graphene is formed. It is difficult to control the precipitation of carbon atoms during the cooling process because the solubility of carbon atoms in nickel increases with temperature, so it has a negative effect on the preparation of graphene. In the case of copper, the solubility of carbon atoms in copper is relatively low at high temperature; therefore, compared with other catalysts, Cu is currently the most widely used catalyst material [22, 45].

4.2. Effect of hydrogen

Hydrogen is often involved in CVD graphene synthesis. Thus, hydrogen has a great impact on graphene reducing substrate surface contamination and defects in the annealing process [59], controlling the graphene domain shape [40, 60, 61], nucleation [62], and layer number [63]. And excess hydrogen could etch graphene to destroy the integrity of the lattice and make the quality of graphene worse [64]. It also affects the adsorption, stability, thickness [65, 66, 67], population of active species on the catalyst surface [68, 69] and the morphology [70, 71, 72, 73, 74, 75, 76, 77, 78, 79] of the grown graphene. Luo et al. [72] determined the effect of hydrogen on the shape and orientation of graphene using DFT calculation (shown in Figure 7). High hydrogen concentration is required to synthesize large single-crystal monolayer graphene domains [40, 80]. Besides the low carbon concentration, etching by hydrogen is also an obstacle to short-time graphene growth [81].

Figure 5.

HRTEM image of single-layer graphene.

4.3. Effect of oxygen

It is known that oxygen plays an important role in each step of graphene synthesis, especially on copper. The effect of surface oxygen or pre-adsorbed oxygen on methane decomposition on Cu and that on the transition metal surface such as Ni and Pd is different [33].

The strong binding of active carbon species with catalyst surface is crucial for nucleation of graphene. The adsorption of active species on the catalyst surface becomes higher in the presence of oxygen. Hao et al. [82] found that the graphene edge with H-termination is better than a bare edge on Cu. In addition, oxygen plays a vital role in reducing the nucleation density not only in the bulk but also on the surface [83].For example, oxygen could remove the unwanted carbon from Cu bulk, [84] which results in unintentional nucleation.

4.4. Effect of gas flow rate

The gas flow has been considered as a crucial factor during graphene synthesis. Optimizing the flow rate of CH4 and H2 could improve the quality of graphene. Therefore, Li et al. [22] described the CVD growth of graphene single crystals up to 0.5 mm in size in a quasi-static flow regime, using a copper enclosure in LPCVD. Meantime, Wang et al. [85] have used a H2flow rate of 20 sccm adopt, at 80 Pa, and 1000°C, in their CVD method for graphene growth. The methane flow was varied systematically between 0.4 and 15 sccm. The graphene was characterized by Raman spectroscopy, and the results were shown in Figure 8. The study found that the ratio of IG/I2D peak ratio did not increase with the increase of methane flow and is less than 0.5. This indicates the formation of single layer graphene and no dependence on methane flow rate. They reported that the methane flow has a significant effect on the structure of graphene and determined the optimal flow rate of methane as 5 sccm. At 0 sccm, ID/I2D peak intensity ratio has a minimum value (0.0395) yielding graphene with the least defects.

Figure 6.

The schematic diagram of APCVD. Reproduced with permission of ref. [54].

Advertisement

5. Timeline of graphene production

Li et al. [22] synthesize large-area graphene grown by low-pressure chemical vapor deposition in copper-foil enclosures using methane as a precursor single crystal with dimensions of up to 0.5 mm on a side. While Hao et al. [82] enabled repeatable growth of centimeter-scale single-crystal graphene domains to attain 1 cm single-crystal graphene by controlling of surface oxygen. Correspondingly, Wu et al. [29] prepare a similar to 1.5-inch-large graphene monolayer in 2.5 h by locally feeding carbon precursors to a desired position of a substrate composed of an optimized Cu-Ni alloy. Besides, Nguyen et al. [86] have fabricated the 6 × 3 cm2 graphene film without grain boundaries on polished copper(111) foil by Seamless stitching of graphene domains. However, a foundation of the modern technology by Xu et al. [34] that using single-crystal silicon improve the growth of high-quality single-crystal graphene with diameters up to 12 inches or larger.

In 2004, micron-sized graphene was obtained by exfoliation, which was not scalable. In 2006, the scientists obtained graphene by thermal deposition of SiC, which is an expensive process. In 2009, researchers first used Cu-CVD method to get graphene, and subsequently, this CVD method was extended to using other metals as substrates.

The graphene can be transferred using a wet method [32]. The process involves (1) coating a protective layer (e.g., PMMA) on one side, (2) etching graphene on the other side, (3) etching away the copper and then rinse with water, (4) transferring to target substrate, and (5) removal of protective film, by typically using solvent to dissolve it. With the development of graphene production, there are many ways to transfer graphene, including R2R ([87, 88, 89], shown in Figure 9) with thermal release tape, R2R with epoxy [90], and bubbling transfer [91]. These developments have led to much more controllable graphene synthesis [19, 33, 89].

Figure 7.

Schematic diagram of Etching-controlled growth mechanism of CVD. Reproduced with permission of ref. [71].

Figure 8.

Raman spectra (a) and Gand 2D peaks (b) of the graphene films grown under various methane fluxes. Reproduced with permission of ref. [85].

Figure 9.

Schematic diagram of roll to roll production of graphene. Reproduced with permission of ref. [89].

Advertisement

6. Development trend and application prospect of CVD graphene

As for the graphene synthesis by CVD, it is beneficial to maximize the scale while maintaining the homogeneity of large-area films, as indicated by Bae et al. [89]. A creative approach to the CVD synthesis of ultra large-area graphene based on selective Joule heating was reported by Kobayashi et al. [92]. Since the first growth on copper foil a decade ago, inch-sized single-crystal graphene has been achieved. For most industrialized applications, large single-crystal graphene films are promising for top-down processing. In recent decades, the SCG island size has increased more than four orders of magnitude, from micrometers to inches. Xu et al. [34] have made large-area graphene film (5 cm × 50 cm) within 20 min, which is almost 99% ultra-highly oriented grains and is, to the best of our knowledge, the largest graphene area synthesized and demonstrated by far. The growth steps are described as follows: (1) manufacturing substrate with meter-sized single-crystal Cu(111) foil; (2) epitaxial growth of graphene grains on the Cu(111) surface; (3) seamless merging of graphene domains into a film with high-single crystallinity; and (4) the growth of graphene film in an ultrafast fashion.

At present, the process of preparing graphene by chemical vapor deposition has matured to the point of large-scale production and has been applied to electric ink, lithium battery additives, coatings and composite materials additives, touch screen, and other low-end applications [93].

For lithium battery applications, graphene as a conductive additive can also solve the contradiction between the high-voltage real ratio and the battery performance of the cathode materials such as lithium cobalt oxide [94]. Graphene has extremely high thermal conductivity, high thermal radiation coefficient, and high specific surface area, so that a surface coating of graphene as auxiliary heat dissipation has great potential for application [95]. Graphene can be used as the main filling material for new conductive ink and plastics [96], and it can also be mixed with nanometer silver powder into a new type of conductive adhesive or ink, and the resistivity and adhesion properties of conductive ink can be adjusted by changing the filling ratio of graphene. The two-dimensional structure of graphene allows for conductive thermal channels in graphene-based anticorrosive paint coating and forms a tight labyrinth of physical barriers to prevent corrosion related exposure. Graphene could be applied to improve performance on graphene capacitive screen [96]. Similarly, carbon nanowalls [97] described as a graphite nano-structure with edge structure and arranged perpendicularly to the matrix on a sheet of graphite have been synthesized by the CVD and is widely used in electrochemical devices, catalyst carriers, etc.

Advertisement

7. Summary and outlook

With excellent prosperities of graphene, there are tremendous amount of research on digging out its exceptional prospect in future applications. But challenges including the growth rate of graphene growth, defects, stacking order, and transfer still remain. Nevertheless, more and more scientific communities are making efforts to achieve the industrialization of graphene. Undoubtedly, the graphene industry is growing at a fast rate. In the next 5–10 years, the technology for graphene-based conductive additives, anticorrosive coatings, touch screen would be mature, along with the industrialization of high-end applications such as super capacitors, sensors, and electronic chips. But mono-crystalline graphene films are extremely difficult to prepare. At present, they can only be made in millimeter size, and they are still quite far away from the practical crystal size, which is difficult to break in the short term. We need to achieve a balance between the advantages and disadvantages of graphene in order to create a fast and healthy way for the sustainable development of graphene. Chemical vapor deposition (CVD) is the most promising preparation technique. The preparation by chemical vapor deposition has become a major method for preparing semiconductor, thin film materials, and industrial production of high-quality graphene materials in large quantity. Meantime, for the CVD method, considerable efforts have been exerted to get low cost on any arbitrary substrate, but it is still a long way to make it.

References

  1. 1. Novoselov KS, Geim AK, Morozov SV, Jiang D, Katsnelson MI, Grigorieva IV, et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature. 2005;438:197-200
  2. 2. Liu Y, Xie B, Zhang Z, et al. Mechanical properties of graphene papers. Journal of the Mechanics & Physics of Solids. 2012;60(4):591-605
  3. 3. Stöberl U, Wurstbauer U, Wegscheider W, et al. Morphology and flexibility of graphene and few-layer graphene on various substrates. Applied Physics Letters. 2008;93(5):19912
  4. 4. Mišković-Stanković V, Jevremović I, Jung I, et al. Electrochemical study of corrosion behavior of graphene coatings on copper and aluminum in a chloride solution. Carbon. 2014;75(10):335-344
  5. 5. Raman RKS, Banerjee PC, Lobo DE, et al. Protecting copper from electrochemical degradation by graphene coating. Carbon. 2012;50(11):4040-4045
  6. 6. Nayak PK, Hsu CJ, Wang SC, et al. Graphene coated Ni films: A protective coating. Thin Solid Films. 2013;529(2):312-316
  7. 7. Ma Y, Kim D, Jang H, et al. Characterization of low temperature graphene synthesis in inductively coupled plasma chemical vapor deposition process with optical emission spectroscopy. Journal of Nanoscience & Nanotechnology. 2014;14(12):9065
  8. 8. Ning G, Xu C, Cao Y, et al. Chemical vapor deposition derived flexible graphene paper and its application as high performance anodes for lithium rechargeable batteries. Journal of Materials Chemistry A. 2012;1(2):408-414
  9. 9. Chen Z, Ren W, Gao L, et al. Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. Nature Materials. 2011;10(6):424
  10. 10. Yuan GD, Zhang WJ, Yang Y, et al. Graphene sheets via microwave chemical vapor deposition. Chemical Physics Letters. 2009;467(4):361-364
  11. 11. Zheng Q, Kim JK. Synthesis, structure, and properties of graphene and graphene oxide. Journal of Experimental Medicine. 2015;23(2):29-94
  12. 12. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, et al. Electric field effect in atomically thin carbon films. Science. 2004;306:666-669
  13. 13. Geim AK. Graphene: Status and prospects. Science. 2009;324:1530-1534
  14. 14. Schwierz F. Graphene transistors. Nature Nanotechnology. 2010;5:487-496
  15. 15. Hernandez Y, Nicolosi V, Lotya M, et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotechnology. 2008;3(9):563-568
  16. 16. Ciesielski A, Samori P. Graphene via sonication assisted liquid-phase exfoliation. Chemical Society Reviews. 2014;43:381-398
  17. 17. Dikin DA, Stankovich S, Zimney EJ, Piner RD, Dommett GHB, Evmenenko G, et al. Preparation and characterization of graphene oxide paper. Nature. 2007;448:457-460
  18. 18. Eda G, Fanchini G, Chhowalla M. Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. Nature Nanotechnology. 2008;3:270-274
  19. 19. Li M, Liu D, Wei D, et al. Controllable synthesis of graphene by plasma-enhanced chemical vapor deposition and its related applications. Advanced Science. 2016;3(11):1600003
  20. 20. Qi Y, Eskelsen JR, Mazur U, et al. Fabrication of graphene with CuO islands by chemical vapor deposition. Langmuir the ACS Journal of Surfaces & Colloids. 2012;28(7):3489-3493
  21. 21. Sun J, Lindvall N, Cole MT, et al. Low partial pressure chemical vapor deposition of graphene on copper. IEEE Transactions on Nanotechnology. 2012;11(2):255-260
  22. 22. Li X, Cai W, An J, et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science. 2009;324(5932):1312
  23. 23. Kwon H-J et al. Synthesis of flake-like graphene from nickel-coated polyacrylonitrile polymer. Nanoscale Research Letters. 2014;9(1):618
  24. 24. Kim M-S et al. Effect of copper surface pre-treatment on the properties of CVD grown graphene. AIP Advances. 2014;4(12):127107
  25. 25. Gnanaprakasa TJ et al. The role of copper pretreatment on the morphology of graphene grown by chemical vapor deposition. Microelectronic Engineering. 2015;131:1-7
  26. 26. Vinogradov NA et al. Formation and structure of graphene waves on Fe(110). Physical Review Letters.2012;109:026101
  27. 27. Sutter P, Sadowski JT, Sutter E. Graphene on Pt(111): Growth and substrate interaction. Physical Review. 2009;B80:245411
  28. 28. Feng X, Wu J, Bell AT, Salmeron M. An atomicscale view of the nucleation and growth of graphene islands on Pt surfaces. Journal of Physical Chemistry C. 2015;119:7124-7129
  29. 29. Wu T et al. Fast growth of inch-sized single-crystalline graphene from a controlled single nucleus on Cu–Ni alloys. Nature Materials. 2015;15(1):43
  30. 30. Liu X, Fu L, Liu N, Gao T, Zhang Y, Liao L. Segregation growth of graphene on Cu–Ni alloy for precise layer control. Journal of Physical Chemistry C. 2011;115:11976-11982
  31. 31. Robertson SD. Graphite formation from low temperature pyrolysis of methane over some transition metal surfaces. Nature. 1969;221(5185):1044-1046
  32. 32. Jiao L, Fan B, Xian X, et al. Creation of nanostructures with poly(methyl methacrylate)-mediated nanotransfer printing. Journal of the American Chemical Society. 2008;130(38):12612-12613
  33. 33. Addou R et al. Monolayer graphene growth on Ni(111) by low temperature chemical vapor deposition. Applied Physics Letters.
  34. 34. Xu X, Zhang Z, Dong J, et al. Ultrafast epitaxial growth of metre-sized single-crystal graphene. Science Bulletin. 2017;62(15):1074-1080
  35. 35. Wang H, Wang G, Bao P, et al. Controllable synthesis of submillimeter single-crystal monolayer graphene domains on copper foils by suppressing nucleation. Journal of the American Chemical Society. 2012;134(8):3627
  36. 36. Fan L, Li Z, Li X, et al. Controllable growth of shaped graphene domains by atmospheric pressure chemical vapour deposition. Nanoscale. 2011;3(12):4946-4950
  37. 37. Liu L, Zhou H, Cheng R, et al. High-yield chemical vapor deposition growth of high-quality large-area AB-stacked bilayer graphene. Acs Nano. 2012;6(9):8241-8249
  38. 38. Yu Q, Jauregui LA, Wu W, et al. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nature Materials. 2010;10(6):443-449
  39. 39. Luo B, Chen B, Meng L, Geng D, et al. Layer-stacking growth and electrical transport of hierarchical graphene architectures. Advanced Materials. 2014;26:3218-3224
  40. 40. Wu B, Geng D, Xu Z et al. Self-organized graphene crystal patterns. NPG Asia Materials. 2013;S:e36
  41. 41. Lotya M, Hernandez Y, King PJ, et al. Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions. Journal of the American Chemical Society. 2009;131(10):3611-3620
  42. 42. Hummers WS, Offeman RE. Preparation of graphitic oxide. Journal of the American Chemical Society. 1958;80(6):1339
  43. 43. Song HS, Li SL, Miyazaki H, Sato S, Hayashi K, Yamada A, et al. Origin of the relatively low transport mobility of graphene grown through chemical vapor deposition. Scientific Reports. UK. 2012;2:337
  44. 44. Muñoz R, Gómez-Aleixandre C. Review of CVD synthesis of graphene. Chemical Vapor Deposition. 2013;19(10-11-12):297-322
  45. 45. Li X, Cai W, Colombo L, Ruoff RS. Evolution of graphene growth on Ni and Cu by carbon isotope labeling. Nano Letters. 2009;9:4268-4272
  46. 46. Van Bommel AJ, Crombeen JE, Van Tooren A. LEED and Auger electron observations of the SiC(0001) surface. Surface Science. 1975;48(2):463-472
  47. 47. Berger C et al. Ultrathin epitaxial graphite: 2D electron gas properties and a route toward graphene-based nanoelectronics. The Journal of Physical Chemistry B. 2004;108(52):19912-19916
  48. 48. Zhang X, Li H, Ding F. Self-assembly of carbon atomson transition metal surfaces—Chemical vapor deposition growth mechanism of graphene. Advanced Materials. 2014;26:5488-5495
  49. 49. Kwon S-Y, Ciobanu CV, Petrova V, Shenoy VB, Bareno J, Gambin V, et al. Growth of semiconducting graphene on palladium. Nano Letters. 2009;9:3985-3390
  50. 50. Losurdo M, Giangregorio MM, Capezzuto P, Bruno G. Graphene CVD growth on copper and nickel: Role of hydrogen in kinetics and structure. Physical Chemistry Chemical Physics. 2011;13:20836-20843
  51. 51. Nie S, Bartelt NC, Wofford JM, Dubon OD, McCarty KF, Thurmer K. Scanning tunneling microscopy study of graphene on Au(111): Growth mechanisms and substrate interactions. Physical Review B. 2012;85:205406
  52. 52. Li Z et al. Low-temperature growth of graphene by chemical vapor deposition using solid and liquid carbon sources. ACS Nano. 2011;5(4):3385-3390
  53. 53. Jang J et al. Low-temperature-growth continuous graphene films from benzene by chemical vapor deposition at ambient pressure. Scientific Reports. 2015;5:17955
  54. 54. Jiang B-B, Pan M, Wang C, Wu MH, Vinodgopal K, Dai G-P. Controllable synthesis of circular graphene domains by atmosphere pressure chemical vapor deposition. Journal of Physical Chemistry C. 2018;122:13572-13578
  55. 55. Weatherup RS, Dlubak B, Hofmann S. Kinetic control of catalytic CVD for high-quality graphene at low temperatures. ACS Nano. 2012;6(11):9996-10003
  56. 56. Yokoyama H, Numakura H, Koiwa M. The solubility and diffusion of carbon in palladium. Acta Materials. 1998;46(8):2823-2830
  57. 57. Sutter PW, Flege JI, Sutter EA. Epitaxial graphene on ruthenium. Nature Materials. 2008;7(5):406-411
  58. 58. Shu N, Bartelt NC, Starodub E, Walter A, Bostwick A, Rotenberg E. Growth from below: Graphene multilayers on Ir(111). United States. 2011. DOI: 10.1021/nn103582g
  59. 59. Loginova E, Bartelt NC, Feibelman PJ, McCarty KF. Evidence for graphene growth by C cluster attachment. New Journal of Physics. 2009;11:063046 (093026)
  60. 60. Yan Z, Lin J, Peng ZW, Sun ZZ, Zhu Y, Li L, Xiang CS, Samuel EL, Kittrell C, Tour JM. ACS Nano. 2012;10(6):126-132
  61. 61. Zhang Y, Li Z, Kim P, Zhang LY, Zhou CW. ACS Nano. 2012;7(6):871-877
  62. 62. Meca E, Lowengrub J, Kim H, Mattevi C, Shenoy VB. Epitaxial graphene growth and shape dynamics on copper: Phase-field modeling and experiments. Nano Letters. 2013;11(13):5692-5697
  63. 63. Jacobberger RM, Arnold MS. Graphene growth dynamics on epitaxial copper thin films. Chemistry of Materials. 2013;6(25):3040-3047
  64. 64. Park HJ et al. Growth and properties of few-layer graphene prepared by chemical vapor deposition. Carbon. 2010;48(4):1088
  65. 65. Zhang X, Wang L, Xin JH, et al. The role of hydrogen in graphene chemical vapor deposition (CVD) growth on copper surface. Journal of the American Chemical Society. 2014;136(8):3040-3047
  66. 66. Weiss SJ, Young J, Lobuglio AF, et al. Role of hydrogen peroxide in neutrophil-mediated destruction of cultured endothelial cells. Journal of Clinical Investigation. 1981;68(3):714-721
  67. 67. Liu Q, Gong Y, Wilt JS, et al. Synchronous growth of AB-stacked bilayer graphene on Cu by simply controlling hydrogen pressure in CVD process. Carbon. 2015;93:199-206
  68. 68. Shu H, Tao XM, Ding F. What are the active carbon species during graphene chemical vapor deposition growth? Nanoscale. 2015;7(5):1627-1634
  69. 69. Li K, He C, Jiao M, et al. A first-principles study on the role of hydrogen in early stage of graphene growth during the CH4 dissociation on Cu(111) and Ni(111) surfaces. Carbon. 2014;74(10):255-265
  70. 70. Gan CK, Srolovitz DJ. First-principles study of graphene edge properties and flake shapes. 2010;81(12):760-762
  71. 71. Geng D, Wu B, Guo Y, et al. From the cover: Uniform hexagonal graphene flakes and films grown on liquid copper surface. Proceedings of the National Academy of Sciences of the United States of America. 2012;109(21):7992-7996
  72. 72. Luo B, Gao E, Geng D, et al. Etching-controlled growth of graphene by chemical vapor deposition. Chemistry of Materials. 2017;29(3):1022-1027
  73. 73. Zhang H, Zhang Y, Zhang Y, et al. Realizing controllable graphene nucleation by regulating the competition of hydrogen and oxygen during chemical vapor deposition heating. Physical Chemistry Chemical Physics. 2016;18(34):23638-23642
  74. 74. Ma T, Ren W, Liu Z, et al. Repeated growth-etching-regrowth for large-area defect-free single-crystal graphene by chemical vapor deposition. ACS Nano. 2014;8(12):12806-12813
  75. 75. Da HJ, Kang C, Kim M, et al. Effects of hydrogen partial pressure in the annealing process on graphene growth. Journal of Physical Chemistry C. 2015;118(7):3574-3580
  76. 76. Hu B, Jin Y, Guan D, et al. H2-dependent carbon dissolution and diffusion-out in graphene chemical vapor deposition growth. Journal of Physical Chemistry C. 2015;119(42):585080264
  77. 77. Jin Y, Hu B, Wei Z, et al. Roles of H2 in annealing and growth times of graphene CVD synthesis over copper foil. Journal of Materials Chemistry A. 2014;2(38):16208-16216
  78. 78. Wu B, Geng D, Guo Y, et al. Equiangular hexagon-shape-controlled synthesis of graphene on copper surface. Advanced Materials. 2011;23(31):3522-3525
  79. 79. Zhao P, Cheng Y, Zhao D, et al. The role of hydrogen in oxygen-assisted chemical vapor deposition growth of millimeter-sized graphene single crystals. Nanoscale. 2016;8(14):7646
  80. 80. Shin YC, Kong J. Carbon. 2013;59:439
  81. 81. Zhang XY, Wang L, Xin J, Yakobson BI, Ding F. Journal of American Chemical Society. 2014;18:136
  82. 82. Hao Y, Ruoff RS. The role of surface oxygen in the growth of large single-crystal graphene on copper. Science. 2013;342(6159):720-723
  83. 83. Liang T, Luan C, Chen H, et al. Exploring oxygen in graphene chemical vapor deposition synthesis. Nanoscale. 2017;9(11):3719
  84. 84. Zhang Y, Li Z, Kim P, Zhang LY, Zhou CW. ACS Nano. 2012;7:6
  85. 85. Wang ZG, Chen YF, Li PJ, et al. Effects of methane flux on structural and transport properties of CVD-grown graphene films. Vacuum. 2012;86(7):895
  86. 86. Nguyen VL, Shin BG, Duong DL, et al. Seamless stitching of graphene domains on polished copper (111) foil. Advanced Materials. 2015;27(8):1376-1382
  87. 87. Yamada T, Ishihara M, Hasegawa M. Large area coating of graphene at low temperature using a roll-to-roll microwave plasma chemical vapor deposition. Thin Solid Films. 2013;532(532):89-93
  88. 88. Juang ZY, Wu CY, Lu AY, et al. Graphene synthesis by chemical vapor deposition and transfer by a roll-to-roll process. Carbon. 2010;48(11):3169-3174
  89. 89. Bae S, Kim H, Lee Y, Xu X, Park J-S, Zheng Y, et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nature Nanotechnology. 2010;5:574
  90. 90. Kraus J, Böbel M, Günther S. Suppressing graphene nucleation during CVD on polycrystalline Cu bycontrolling the carbon content of the support foils. Carbon. 2016;96:153-165
  91. 91. Zhang H, Zhang Y, Wang B, Chen Z, Sui Y, Zhang Y, et al. Journal of Electronic Materials. 2015;44:79-86
  92. 92. Kobayashi T, Bando M, Kimura N, Shimizu K, Kadono K, Umezu N, et al. Production of a 100-m-long high-quality graphene transparent conductive film by roll-to-roll chemical vapor deposition and transfer process. Applied Physics Letters. 2013;102:023112
  93. 93. Choi W, Lahiri I, Seelaboyina R, Kang YS. Synthesis of graphene and its applications: A review. Critical Reviews in Solid State and Materials Sciences. 2010;35:52-71
  94. 94. Li X, Sun X, et al. A simple one-pot strategy for synthesizing ultrafine SnS2 nanoparticle/graphene composites as anodes for lithium/sodium-ion batteries. ChemSuschem. 2018;11(9):1390-1575
  95. 95. Molina-Valdovinos S et al. Low-dimensional thermoelectricity in graphene: The case of gated graphene superlattices. Physica E: Low-dimensional Systems and Nanostructures. 2018;101:188-196
  96. 96. Arapov K et al. Conductive screen printing inks by gelation of graphene dispersions. Advanced Functional Materials. 2016;26(4):586-593
  97. 97. Wang JJ, Zhu MY, Outlaw RA, Zhao X, Manos DM. Free-standing sub-nanometer graphite sheets. Applied Physics Letters. 2004;85:1265

Written By

Chen Wang, Kizhanipuram Vinodgopal and Gui-Ping Dai

Submitted: 22 February 2018 Reviewed: 05 July 2018 Published: 05 November 2018

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Continue reading from the same book

View All
Chapter 6 Atmospheric Pressure Chemical Vapor Deposition of ...

By Phuong V. Pham

2002 downloads

Chapter 7 Chemical Vapor Deposition of Helical Carbon Nanofi...

By Yoshiyuki Suda

1517 downloads

Chapter 1 Spatial Atomic Layer Deposition

By David Muñoz-Rojas, Viet Huong Nguyen, César Masse ...

2249 downloads