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• Published: 18 March 2022

Large-scale synthesis of graphene and other 2D materials towards industrialization

• Soo Ho Choi   ORCID: orcid.org/0000-0002-9927-0101 1 , 2   na1 ,
• Seok Joon Yun 1 , 2   na1 ,
• Yo Seob Won 2 ,
• Chang Seok Oh 2 ,
• Soo Min Kim 3 ,
• Ki Kang Kim   ORCID: orcid.org/0000-0003-1008-6744 1 , 2 &
• Young Hee Lee   ORCID: orcid.org/0000-0001-7403-8157 1 , 2  

Nature Communications volume  13 , Article number:  1484 ( 2022 ) Cite this article

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• Electronic devices
• Synthesis and processing
• Synthesis of graphene
• Two-dimensional materials

The effective application of graphene and other 2D materials is strongly dependent on the industrial-scale manufacturing of films and powders of appropriate morphology and quality. Here, we discuss three state-of-the-art mass production techniques, their limitations, and opportunities for future improvement.

Two-dimensional (2D) van der Waals (vdW) layered materials including graphene, transition metal dichalcogenides (TMDs), hexagonal boron nitride (hBN), and MXenes have attracted much attention in recent years. This is due to their distinctive physical and chemical properties, such as their quantum Hall effects and quantum valley Hall effects, indirect-to-direct bandgap transition, and strong spin-orbit coupling 1 , which have not been accessible with conventional 3D bulk materials. In addition, vertical vdW heterostructures constructed by layer-by-layer stacking enable interesting applications for atomically thin quantum wells, p-n junctions, Coulomb drag transistors, and twistronic devices 1 , 2 , 3 . However, applications based on such structures are limited by the fact that most vdW materials are currently only available with a lateral size of up to a few tens of micrometers. Techniques for the large-scale synthesis of 2D materials will therefore be required for industrialization. Moreover, since specific applications of these materials are strongly dependent on characteristics such as their morphology and quality, mass production techniques should also be developed that can accommodate such requirements (Fig.  1 ). In general, most applications rely on either films or powders of vdW materials. Films require high crystal quality, and can be used in the context of electronics, spintronics, optoelectronics, twistronics, or solar cells, whereas powders exhibit large surface areas and are employed in the construction of batteries, sensors, and catalysts. At present, only large-area graphene films and graphite oxide powders are currently available in the commercial market 4 . In this Comment, we briefly examine research trends in synthesis techniques and their associated challenges for the industrialization of 2D layered materials.

2D films and heterostructures require high crystal quality and homogeneous thickness for applications such as electronics and spintronics, whereas high-porosity powders with vast specific surface area can be used in contexts such as catalysts and energy storage.

Three representative synthesis techniques

There are currently three representative synthesis techniques available for the large-scale synthesis of 2D materials. The first is chemical vapor deposition (CVD); although a variety of thin-film deposition techniques have been investigated for growing large-area 2D films, including pulsed laser deposition (PLD) 5 , atomic layer deposition (ALD) 6 , and molecular beam epitaxy (MBE) 7 , CVD is most feasible for industrialization when one takes into account the uniformity and crystallinity of 2D films as well as requirements of high throughput, cost effectiveness, and scalability. The other two techniques being investigated for mass production are top-down liquid exfoliation of 2D materials and bottom-up wet chemical synthesis.

CVD for growing large-scale 2D thin films

There are multiple examples of CVD synthesis of thin films at wafer scale (Fig.  2a ). For example, wafer-scale polycrystalline monolayer and multilayer graphene films have been successfully synthesized by CVD on polycrystalline Cu and Ni foils since 2009 8 , 9 , 10 , 11 , and wafer-scale single-crystal monolayer graphene has been synthesized by using single-crystal substrates such as H–Ge (110) and Cu (111) 12 , 13 . Single-crystal multilayer graphene films have been also grown on Si–Cu alloys at wafer scale 14 . In 2012, centimeter-scale polycrystalline monolayers of hBN and TMDs were grown on polycrystalline Cu foils and SiO 2 /Si substrates, respectively 15 , 16 . And more recently, single-crystal hBN and TMD films were successfully synthesized on liquid Au, high-index single-crystal Cu surfaces, and atomic sawtooth Au surfaces 17 , 18 .

Lefthand panels show timelines of milestones for a chemical vapor deposition (CVD), b liquid exfoliation, and c wet chemical synthesis methods. The abbreviations correspond to: metal-organic CVD (MOCVD), graphene (Gr), graphite oxide (GO), reduced GO (rGO), and molybdenum disulfide (MoS 2 ). Righthand panels show the corresponding strengths and weaknesses of these methods in terms of mass production (MP), thickness controllability (THK), temperature variation (TEMP), uniformity (UNI), material diversity (MAT), crystal quality (QLTY), morphology (MORPH). Panel a reprinted from refs. 9 , 17 , American Association for the Advancement of Science, ref. 15 , Nature, refs. 7 , 10 , 12 , Wiley, ref. 5 , American Institute of Physics, ref. 6 , Royal Society of Chemistry, and ref. 11 , World Scientific. Panel b reprinted from refs. 26 , 27 , American Association for the Advancement of Science, refs. 22 , 23 , Wiley, refs. 19 , 20 , 21 , Elsevier, and ref. 24 , Institute of Electrical and Electronic Engineers. Panel c reprinted from ref. 28 , Elsevier, ref. 30 , American Chemical Society, ref. 31 , Elsevier, and ref. 32 , Royal Society of Chemistry.

CVD produces relatively high-quality 2D films under atmospheric or low pressure, and the size of the film can easily be scaled up by increasing the chamber size. However, high temperature reactions (above 500 °C) are required, which could be a drawback for industrialization. The growth of a vast range of 2D materials, including graphene, hBN, and TMDs, is still limited by the absence of appropriate precursors. Perhaps the most important technical challenge presented by this method is the poor control over the number of synthesized layers, because the absence of dangling bonds on the surface of 2D vdW materials makes epitaxial growth difficult.

Liquid exfoliation

Liquid exfoliation is a powerful process for the mass production of pristine 2D bulk materials by dispersing them into individual sheets. Bulk materials have been synthesized by chemical vapor transport (CVT) (Fig.  2b ) since the late 1960s, but most 2D bulk materials are currently only available in small quantities. Nanodispersion into monolayers is often required to manifest the unique 2D nature, but the strong vdW energy of micron-scale materials hinders facile exfoliation. Thus, two additional steps should be considered for liquid exfoliation processes: (i) weakening the layer-layer interaction by expanding the interlayer distance, and (ii) physical agitation for dispersion 19 , 20 . In 1958, it was demonstrated that the interlayer distance can be increased from 3.4 to 7.0 Å by the oxidation of graphite, known as “graphite oxide”, and such an expansion of the interlayer distance made it possible to disperse the individual graphite oxide layers by sonication. Graphite oxide layers can subsequently be reduced to graphene nanosheets through chemical treatment with reducing agents and thermal annealing treatment 21 , 22 , 23 .

The lattice of graphene nanosheets is often severely damaged during oxidation and reduction processes. To prevent this, the interlayer distance can be increased by intercalating ions and molecules between layers. Electrochemistry enables effective intercalation of both cations and anions in an electrolyte solution by applying negative and positive bias, respectively 24 . Alkali metals, organic solvents, and surfactants with similar surface energies to those of the 2D materials can also be directly intercalated in liquid or vapor phase 25 , 26 . After intercalation, agitation methods such as sonication, homogenization, and microwave treatment can be employed to exfoliate materials into individual 2D layers 27 . Liquid exfoliation enables mass production of 2D nanosheets under atmospheric pressure at room temperature. However, this approach also leads to presumably unavoidable damage and non-uniform nanosheet thickness.

Wet chemical synthesis

Hydrothermal and solvothermal syntheses are representative wet chemical synthesis methods, in which materials are respectively solubilized in aqueous solution and organic solvent under high vapor pressure at elevated temperatures (~300 °C). A variety of nanomaterials have been synthesized in this fashion since the first report of hydrothermal synthesis of microscopic quartz crystals in 1845 (Fig.  2c ). The wet chemical synthesis of pure 2D materials such as graphene and MoS 2 surged in the early 21st century 28 , 29 , and more recently, doped 2D materials, nanocomposites, and their heterostructures have been synthesized in this fashion by adding various precursors and dopants in solvent to enhance the material properties for specific applications 30 , 31 , 32 , 33 . For example, the hydrogen evolution reaction in graphene oxide was dramatically enhanced by introducing boron dopants 33 .

The strengths of wet chemical synthesis include the controllability of surface morphology, crystallite size, and dopants in 2D materials for catalyst, energy storage, and chemical/biological sensor applications. Reaction temperatures, precursors, and additives have been optimized for various types of 2D materials and their composites, enabling essentially unlimited mass production. The direct synthesis of 2D materials on a desired substrate is also possible, although such synthesis takes a relatively longer time—up to a few days. Growth temperature is often limited to below 300 °C due to the limited durability of equipment under harsh conditions including high pressure and exposure to corrosive chemicals. It is worth noting that bottom-up synthesis tends to yield low-quality 2D materials with defects, but it is still possible to employ these for catalytic applications.

Perspectives and challenges toward industrialization

The abovementioned techniques enable mass production of 2D materials, but considerable further advances will be required for some specific applications. Single-crystal graphene films have been successfully synthesized at wafer scale with layer control, but the synthesis of other 2D materials such as hBN and TMDs are limited exclusively to single-crystal monolayer films. Thickness control of such materials is essential for tunneling barrier and high-performance electronics. The combination of tunable bandgap semiconductors, metals, and insulators in 2D systems can generate versatile heterostructures with remarkable physical properties. Several planar and vertical heterostructures have been generated to date, but these remain limited to micron scale 34 , 35 . More generally, the growth of various heterostructures at wafer scale is still challenging (Fig.  3a ). Atomic sawtooth surfaces could be ideal as a growth platform for single-crystal 2D materials including graphene, hBN, TMDs, and their heterostructures, but surface facet control remains elusive. The formation of wrinkles in 2D films after high temperature growth is another important issue, originating from the thermal expansion coefficient mismatch between 2D materials and growth substrate. Recently, the growth of fold-free single-crystal graphene films at 750 °C has been reported 36 , but further investigation will be required to see if this method is applicable for other 2D materials, and lower-temperature growth methods should be established.

a Single-crystal homo/heteroepitaxial growth, wrinkle formation by thermal expansion coefficient mismatch between 2D materials and growth substrates, and cracking/contamination during the transfer process are all issues presented by the CVD technique. b Inhomogeneous size and thickness of 2D nanosheets and poor production yield are problems associated with liquid exfoliation. c Low durability and instability of 2D materials by defects and environmental pollution remain challenges for wet chemical synthesis.

High temperature processes (above 400 °C) are not compatible with current Si technology, and 2D thin films grown by CVD at high temperature must therefore be transferred onto a target substrate. A conventional transfer process can give rise to serious problems such as folding and cracking of 2D films, ultimately degrading film homogeneity and device performance. Furthermore, the polymer contaminants that are commonly introduced as a supporting layer for the transfer process can give rise to unintentional doping and high contact resistance in heterostructure interfaces and devices. Therefore, methods for the direct growth of large-area 2D films by CVD or advanced roll-to-roll transfer technique would be highly desirable. For industrialization, the manufacturing process including scalable techniques (roll-to-roll, batch-to-batch, etc.), production capacity/cost, reproducibility, and large-area uniformity are further considered 37 .

Wet chemical processes including liquid exfoliation and wet chemical synthesis also face several challenges for the mass production of 2D materials. Liquid exfoliation employs pristine 2D bulk materials synthesized by CVT or flux methods for the mass production of 2D nanosheets. Those synthetic methods typically take at least one week, lowering the throughput of production, and companies need the capacity to provide these bulk materials at a larger scale. Additionally, the production yield of liquid exfoliation generally remains poor, and although some materials show relatively high yield, most 2D materials like hBN and telluride are not effectively exfoliated with current techniques. In addition, it is difficult to obtain 2D nanosheets of uniform size and thickness with this method (Fig.  3b ). In order to remedy this, improved techniques for sorting the synthesized nanosheets in terms of size and thickness (e.g., density gradient ultracentrifugation) are needed.

Bottom-up chemical synthesis typically produces 2D materials with low crystal quality. The defect sites (i.e., edges) often serve as active sites for 2D catalyst, but also give rise to low durability and instability issues. Moreover, 2D materials generated by chemical synthesis are not uniformly distributed in terms of size and thickness, requiring special care during synthesis. In addition, the byproducts frequently generated during chemical synthesis can inhibit catalytic activity. To resolve these material quality and byproduct issues, post-treatments such as thermal annealing and purification have been suggested, but a simple process without post-treatment would greatly improve productivity. Another important issue is the environmental pollution caused by the large amount of hazardous chemical wastes used in synthesis (Fig.  3c ), and the use of supercritical fluid regions could be considered as a shortcut to minimize chemical use 38 .

In addition, rapid and reliable non-destructive characterization tools are highly required to evaluate the wafer-scale 2D materials in terms of sample quality and uniformity. The current state-of-the-art terahertz image, phase-shift interferometry, and wide-field Raman imaging could be adopted to analyze the electrical and optical properties of 2D films with short acquisition time of a few seconds per mm 2 and high spatial resolution of an order of micrometers 39 , 40 , 41 . It still requires a prolonged period to thoroughly inspect 12-inch wafer-scale sample, and therefore, the development of advanced characterization tools is further desired.

From a materials point of view, there is plenty of room for unexplored novel 2D materials and their vdW heterostructures. Since it is almost impossible to explore all such materials experimentally, artificial intelligence-based material design could prove useful for the industrialization and large-scale manufacture of such newly-developed 2D materials 42 .

Novoselov, K. S., Mishchenko, A., Carvalho, A. & Neto, A. H. C. 2D materials and van der Waals heterostructures. Science 353 , aac9439 (2016).

Article   CAS   PubMed   Google Scholar  

Jin, Y. et al. Coulomb drag transistor using a graphene and MoS 2 heterostructure. Commun. Phys. 3 , 189 (2020).

Article   CAS   Google Scholar  

Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556 , 43–50 (2018).

Article   ADS   CAS   PubMed   Google Scholar  

Lin, L., Peng, H. L. & Liu, Z. F. Synthesis challenges for graphene industry. Nat. Mater. 18 , 520–524 (2019).

Koh, A. T. T., Foong, Y. M. & Chua, D. H. C. Cooling rate and energy dependence of pulsed laser fabricated graphene on nickel at reduced temperature. Appl. Phys. Lett. 97 , 114102 (2010).

Article   ADS   Google Scholar  

Tan, L. K. et al. Atomic layer deposition of a MoS 2 film. Nanoscale 6 , 10584–10588 (2014).

Park, J. et al. Epitaxial graphene growth by carbon molecular beam epitaxy (CMBE). Adv. Mater. 22 , 4140–4145 (2010).

Zhang, Y., Zhang, L. Y. & Zhou, C. W. Review of chemical vapor deposition of graphene and related applications. Acc. Chem. Res. 46 , 2329–2339 (2013).

Li, X. S. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324 , 1312–1314 (2009).

Chae, S. J. et al. Synthesis of large-area graphene layers on poly-nickel substrate by chemical vapor deposition: Wrinkle formation. Adv. Mater. 21 , 2328–2333 (2009).

Han, G. H. et al. Poly(ethylene co-vinyl acetate)-assisted one-step transfer of ultra-large graphene. Nano 6 , 59–65 (2011).

Nguyen, V. L. et al. Seamless stitching of graphene domains on polished copper (111) foil. Adv. Mater. 27 , 1376–1382 (2015).

Nguyen, V. L. & Lee, Y. H. Towards wafer-scale monocrystalline graphene growth and characterization. Small 11 , 3512–3528 (2015).

Nguyen, V. L. et al. Layer-controlled single-crystalline graphene film with stacking order via Cu–Si alloy formation. Nat. Nanotechnol. 15 , 861–867 (2020).

Kang, K. et al. High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity. Nature 520 , 656–660 (2015).

Cai, Z. Y., Liu, B. L., Zou, X. L. & Cheng, H. M. Chemical vapor deposition growth and applications of two-dimensional materials and their heterostructures. Chem. Rev. 118 , 6091–6133 (2018).

Lee, J. S. et al. Wafer-scale single-crystal hexagonal boron nitride film via self-collimated grain formation. Science 362 , 817–821 (2018).

Choi, S. H. et al. Epitaxial single-crystal growth of transition metal dichalcogenide monolayers via the atomic sawtooth Au surface. Adv. Mater. 33 , 2006601 (2021).

Chen, G. H. et al. Preparation and characterization of graphite nanosheets from ultrasonic powdering technique. Carbon 42 , 753–759 (2004).

Stankovich, S., Piner, R. D., Nguyen, S. T. & Ruoff, R. S. Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets. Carbon 44 , 3342–3347 (2006).

Stankovich, S. et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45 , 1558–1565 (2007).

Shin, H. J. et al. Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance. Adv. Funct. Mater. 19 , 1987–1992 (2009).

Jin, M. H. et al. Facile physical route to highly crystalline graphene. Adv. Funct. Mater. 21 , 3496–3501 (2011).

Kozawa, A., Fujita, K., Sato, A. & Brodd, D. Recent new additives for electric vehicle lead-acid batteries for extending the cycle life and capacity. In Twelfth Annual Battery Conference on Applications and Advances . 277–282 (IEEE, 1997).

Wan, J. Y. et al. Tuning two-dimensional nanomaterials by intercalation: Materials, properties, and applications. Chem. Soc. Rev. 45 , 6742–6765 (2016).

Viculis, L. M., Mack, J. J. & Kaner, R. B. A chemical route to carbon nanoscrolls. Science 299 , 1361–1361 (2003).

Coleman, J. N. et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 331 , 568–571 (2011).

Zhan, J. H. et al. Solvothermal synthesis of nanocrystalline MoS 2 from MoO 3 and elemental sulfur. J. Solid State Chem. 141 , 270–273 (1998).

Article   ADS   CAS   Google Scholar  

Yang, L. S., Chen, W. J., Yu, Q. M. & Liu, B. L. Mass production of two-dimensional materials beyond graphene and their applications. Nano Res 14 , 1583–1597 (2021).

Deng, D. H. et al. Toward N-doped graphene via solvothermal synthesis. Chem. Mater. 23 , 1188–1193 (2011).

Wang, J. et al. Ni 3 S 2 @MoS 2 core/shell nanorod arrays on Ni foam for high-performance electrochemical energy storage. Nano Energy 7 , 151–160 (2014).

Deng, J. et al. Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS 2 surface via single-atom metal doping. Energy Environ. Sci. 8 , 1594–1601 (2015).

Sathe, B. R., Zou, X. X. & Asefa, T. Metal-free B-doped graphene with efficient electrocatalytic activity for hydrogen evolution reaction. Catal. Sci. Technol. 4 , 2023–2030 (2014).

Article   Google Scholar  

Duong, D. L., Yun, S. J. & Lee, Y. H. van der Waals layered materials: Opportunities and challenges. ACS Nano 11 , 11803–11830 (2017).

Li, M. Y., Chen, C. H., Shi, Y. M. & Li, L. J. Heterostructures based on two-dimensional layered materials and their potential applications. Mater. Today 19 , 322–335 (2016).

Wang, M. et al. Single-crystal, large-area, fold-free monolayer graphene. Nature 596 , 519–524 (2021).

Lin, L. & Liu, Z. Synthesis challenges for graphene industry. Nat. Mater. 18 , 520–524 (2019).

Takahashi, Y., Nakauasu, Y., Iwase, K., Kobayashi, H. & Honma, I. Supercritical hydrothermal synthesis of MoS 2 nanosheets with controllable layer number and phase structure. Dalton Trans. 49 , 9377–9384 (2020).

Lee, U. et al. Facile morphological qualification of transferred graphene by phase-shifting interferometry. Adv. Mater. 32 , 2002854 (2020).

Havener, R. W. et al. High-throughput graphene imaging on arbitrary substrates with widefield Raman spectroscopy. ACS Nano 6 , 373–380 (2012).

Scarfe, S., Cui, W., Luican-Mayer, A. & Ménard, J.-M. Systematic THz study of the substrate effect in limiting the mobility of graphene. Sci. Rep. 11 , 8729 (2021).

Article   ADS   CAS   PubMed   PubMed Central   Google Scholar  

Cai, J. Z., Chu, X., Xu, K., Li, H. B. & Wei, J. Machine learning-driven new material discovery. Nanoscale Adv. 2 , 3115–3130 (2020).

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Acknowledgements

K.K.K. acknowledges support by Samsung Research Funding & Incubation Center of Samsung Electronics under Project Number SRFC-MA1901-04, the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2018R1A2B2002302 and 2020R1A4A3079710). K.S.M. acknowledges support by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2022R1A2C2009292). Y.S.J., C.S.H., K.K.K., and L.Y.H. acknowledge support by the Institute for Basic Science (IBS-R011-D1).

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These authors contributed equally: Soo Ho Choi, Seok Joon Yun.

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Center for Integrated Nanostructure Physics, Institute for Basic Science (IBS), Suwon, 16419, Republic of Korea

Soo Ho Choi, Seok Joon Yun, Ki Kang Kim & Young Hee Lee

Department of Energy Science, Sungkyunkwan University, Suwon, 16419, Republic of Korea

Soo Ho Choi, Seok Joon Yun, Yo Seob Won, Chang Seok Oh, Ki Kang Kim & Young Hee Lee

Department of Chemistry, Sookmyung Women’s University, Seoul, 14072, Republic of Korea

Soo Min Kim

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C.S.H., Y.S.J., K.S.M., K.K.K., and L.Y.H. designed and developed this work. W.Y.S., O.C.S., Y.S.J., and C.S.H. investigated the history and technical issues of the various production methods. All authors participated in the writing manuscript.

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Correspondence to Soo Min Kim , Ki Kang Kim or Young Hee Lee .

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Choi, S.H., Yun, S.J., Won, Y.S. et al. Large-scale synthesis of graphene and other 2D materials towards industrialization. Nat Commun 13 , 1484 (2022). https://doi.org/10.1038/s41467-022-29182-y

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Progress in Graphene Synthesis and its Application: History, Challenge and the Future Outlook for Research and Industry

Kartika A. Madurani 1 , Suprapto Suprapto 1 , Nur Izzati Machrita 1 , Setyadi Laksono Bahar 1 , Wihda Illiya 1 and Fredy Kurniawan 1

Published 12 October 2020 • © 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited ECS Journal of Solid State Science and Technology , Volume 9 , Number 9 Citation Kartika A. Madurani et al 2020 ECS J. Solid State Sci. Technol. 9 093013 DOI 10.1149/2162-8777/abbb6f

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Graphene is a thin layer carbon material that has become a hot topic of research during this decade due to its excellent thermal conductivity, mechanical strength, current density, electron mobility and surface area. These extraordinary properties make graphene to be developed and applied in various fields. On this basis, researchers are interested to find out the methods to produce high quality graphene for industrial use. Various methods have been developed and reported to produce graphene. This paper was designed to summarize the development of graphene synthesis methods and the properties of graphene products that were obtained. The application of graphene in the various fields of environment, energy, biomedical, sensors, bio-sensors, and heat-sink was also summarized in this paper. In addition, the history, challenges, and prospects of graphene production for research and industrial purposes were also discussed.

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This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/ ), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: [email protected].

This paper is part of the JSS Focus Issue on 2D Layered Materials: From Fundamental Science to Applications .

Graphene is a type of carbon allotrope that is very popular in the research and industry sector today. 1 – 3 This material has a single layer of carbon atoms and it is the basic structure of other carbon allotropes, such as charcoal, graphite, fullerene and carbon nanotubes. 4 – 6 Graphene have better physical properties compared to other materials, such as high thermal conductivity (5000 Wm −1 K −1 ), 7 high electron mobility (250,000 cm 2 V −1 s −1 ), 8 high Young modulus values (1.0 TPa), 9 large surface area (2630 m 2 g −1 ), 10 and better electrical conductivity and optical transmittance. 11 On this basis, graphene can replace conventional materials in a variety of applications and industries. 10 , 12 – 20

In general, graphene can be synthesized using mechanical exfoliation, 1 , 6 , 21 arc-discharge, 22 – 24 and chemical vapor deposition or CVD. 16 , 25 , 26 Other methods for graphene synthesis were also developed such as chemical reduction, 27 – 29 sonochemicals, 30 – 32 electrochemicals 15 , 33 , 34 and laser ablation. 35 – 37 All these methods were developing very rapidly with various types of modifications being made to produce high quality graphene. The conditions of synthesis and selection of precursor chemicals greatly affect the quality of graphene. This paper reports the progress of the latest methods and their modifications to obtain graphene with good quality. The general history of graphene production and application is explained in this paper. In addition, the challenges and prospects in the production of graphene for research and industrial purposes were also discussed.

Graphene for Research and Industry

Graphene has some excellent properties to make it extremely appealing for applications in many fields such as energy, environment, future material, biomedical, and sensor, bio-sensor and heat-sink (Fig. 1 ). Those wide application shows that graphene has a high commercial value. Taking this into account, the commercial impact of graphene is quite likely to increase in the future. Scientists have also found a way to transform graphene from a material ideal only for fundamental studies to an engineering material, which gives further alternative substantial solutions for industrial and consumer needs. In regard to their applications, research and industry are much related to each other and cannot be separated. Industries cannot develop without research, whereas the results of research will be meaningless if they cannot be utilized in industrially scale. In this section, each of the applications of graphene in several fields is reviewed.

Figure 1.  Graphene application in research and industry.

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Energy fields

One of the main concerns for today is the availability of renewable and clean energy. In response, scientists have made great efforts on seeking and designing materials that have the right properties for energy storage technology. Energy storage technology is found in solar cell, fuel cell, batteries, and supercapacitors. Useful properties of graphene such as high mechanical flexibility, high specific surface area, ultra-thinness, good electrical conductivity, and high theoretical capacitance can be used for energy storage technology. 38 – 40 Graphene have been used and thoroughly researched for lithium ion batteries, flexible or micro-supercapacitors, lithium air batteries, lithium-sulfur batteries, electrode for fuel cell and solar cell. On this basis, ultra-high specific surface area of graphene is needed for large ion storage in electric double layer capacitors, whereas functionalized graphene is needed for anchoring other active species in batteries. Highly flexible and conductive graphene-based membranes may also be used as either interlayers or current collectors in lithium-sulfur batteries. Graphene with a macro porous structure is substantial for catalytic growth/decomposition and accommodation of lithium batteries. 40 – 44

Environmental fields

Environmental protection has also become another major issue during this decade. Environmental issues should receive more attention in order to maintain the sustainability of the planet Earth. Strategies for pollution treatments have received more interest to be researched. Zhao et al., (2012) reported that graphene is a good sorbent, as well as being able to be recycled. 38 It was proven that graphene can adsorb liquids up to 600 times heavier than its own weight. Graphene can also perform exceptionally well when adsorbing gasoline until it reaches an adsorption of 2.77 × 10 2 gg −1 . Other substances that graphene could adsorb include ethanol, olive oil, nitrobenzene, acetone, and dimethyl sulfoxide. Graphene was also investigated for desalination technology. 45 – 49 It should be noted that an essential property of graphene when it comes to environmental treatment and technology is its surface area.

Biomedical fields

Academicians and scientists have been investigating the feasibility of implementing graphene in biomedical industry. 50 It was reported that several outstanding properties of graphene, such as its high opacity, high chemical reaction, and unparalleled thermal conductivity, are suitable for biomedical purposes. The great functional groups of graphene, such as graphene oxide and N-graphene, are being preferred for biomedical application. These functional groups produce high and effective results. 50 As presented in Fig. 1 , graphene is already used in several biomedical applications, such as diagnostic technology, 51 – 55 drug delivery, 56 – 60 therapy technology, 57 , 61 , 62 and scaffolding materials. 63 – 67

A strong reason for using graphene in biomedical purposes is due to its consistency and its ability to develop a uniform structure. The suitability of graphene when it comes to biomedical application depends on its shape, size, morphology, thickness and degree of oxidation. 50 Another suitable property of graphene is its low toxicity, proven by its ability to remain stable for a period of long time in metabolic pathways and during cellular intake. However, further observations are needed on the in vivo process with graphene, especially for drug delivery application. 58 , 68 , 69 For commercialization purposes, biomedical industries should give more attention towards the aforementioned points. Hence for this reason, prior to commercialization, research is needed to be executed which may latterly be used as a basis and evidence to show the benefits of graphene towards major biomedical industries.

Sensor, bio-sensor, and heat-sink application

Graphene is widely used as materials engineering due to its highly appealing properties since its first appearance in 2004. 70 This material can be used as one of active material for Li-ion battery (LIB) anode and electrochemical double-layer capacitor (EDLC) electrode due to its presents a Li + storage capacity of 744 mAh.g −1 and electric double-layer capacitance of 550 F.g −1 . 71 Han et al. in 2020 also reported the polymer composite with vertically graphene architecture. 72 This material is a promising candidate for thermal interface materials due to its thermal conductivity reached 2.18 W·m −1 ·K −1 .

Graphene and its derivatives also can be used as sensor and bio-sensor materials. Bai et al. made a new sensor using reduced graphene oxide (rGO) with combination by polyoxometalates-doped Au nanoparticles for sensing uric acid in urine. 52 The sensor has a low detection limit for uric acid determination, i.e. 8.0 × 10 −8 M. Graphene-based bio-sensor also developed for early detection of Zika virus infection. 53 The bio-sensor response for Zika virus is excellent in buffer condition at concentrations as low as 450 pM. Potential diagnostic applications were applied by measuring the Zika virus in a human serum. Another sensor based on graphene also fabricated by Khalifa et al. in 2020. 73 They made a smart paper from graphene coated cellulose for high-performance humidity and piezoresistive force sensor. The sensor has high piezoresistive response i.e. between 125%–250%. They stated that cellulose paper with low cost, lightweight and biocompatibility combined with graphene could be a promising material for smart, wearable electronic devices. In the other side, graphene is also good material for semiconductor 74 , 75 and electronic device. 76 , 77 Graphene also can be formed as flexible and transparent materials 77 , 78 for various application. The material easy to change become an ink with high conductivity 79 – 83 for injecting printing purposes. Based on described examples, the presence of graphene in the recent times could serve as a future material for various fields especially as sensor, bio-sensor, and heat-sink.

History of Graphene Production

The term graphene consists of the prefix "graph" for graphite and the suffix "-ene" of the C–C double bond. 84 – 86 The term graphene was recommended by Boehm et al. at 1986 and only applies to single layer carbon. 1 , 84 This term was later formalized by The International Union for Pure and applied Chemistry (IUPAC). 41 , 87 Later on, the definition of graphene belongs to a single carbon layer of graphite structure, describing its nature by analog to polycyclic aromatic hydrocarbons of quasi-infinite size. 85 Graphene is also known to be the parent of all carbon allotropes. 10 , 41 , 88 Graphene (2D) being rolled into carbon nanotubes (1D), whereas, if a graphene is being wrapped, it will form a fullerence (0D). In addition, graphite with a 3D structure can be obtained from the graphene build up process. This material can be obtained in various ways where each of the methods performed will produce a different graphene property.

Initially, graphene was reported as a 2D graphite and was theoretically studied over the past 6 decades by Schafheuti, Brodie, Staudenmaier, Hummers, and Wallace, 1 , 89 , 90 where later Wallace's theory was proven by DiVincenzo and Mele in 1984. 84 , 91 They reported that Wallace's electrons hopping conduction could be recasted as massless spin −1/2 particles in a DiracWeyl formalism, an equation used to model neutrinos. The theory explains that electrons behave as if they have an extra degree of freedom, known as pseudospin in the unit cell of the graphene. Furthermore, Semenoff was able to predict anomalous behaviors of graphene with respect to the quantum Hall effect. 91 – 93 Further observations have been reported by Konstantin Novoselov and Andre Geim in 2004, 94 where their experiment included innovative methods in providing new important information in relation to graphene. This useful information caused K. Novoselov and A. Geim to receive the Nobel Prize in Physics in 2010. Since then, graphene has been known as an impressive material with exceptional physical properties (Table I ) in terms of its mechanical, optical, electronic strength and electrochemistry properties. 9 , 11 , 12 , 95 , 96 The timeline of events in the history of graphene is summarized in Fig. 2 . In the future the research will emphasize to find easier route of synthesis with better characteristic. Furthermore, in the industrial perspective, one will consider cost of production and reproducible product to have a standard quality. Graphene can be produced in various forms. 85 In 2013, Bianco et al. proposed the first nomenclature for naming graphene and its derivatives with the aim of making it easier for other researchers to study graphene (Fig. 3 ). 85 , 94 , 97 Figure 3 is various type of graphene equipped with SEM images.

Table I.   The extraordinary properties of graphene.

Figure 2.  A timeline of events in the graphene history. 84 , 91

Figure 3.  Various types of graphene. 98 , 103 – 106 , 107 – 112

The synthesis method can hugely affect the form of the graphene product 113 – 116 as the synthesis process can frequently cause defects in the graphene products. However, not all defects will deteriorate the properties of the graphene as some defects proved to be beneficial. Defects that can be controlled could be useful for some application. Defects that are found in the graphene structures have been studied by several researcher. Defects can be divided into two types, which are point defects and one-dimensional line defects. Liu et al., (2015) have studied the detail of defects in the graphene structure. 116 The examples of point defects are Stoke-Wales disabilities, single vacancies, and pooled vacancies. Meanwhile, the one-dimensional defect is a line defect as slope boundary that separates two domains in different lattice orientations from the normal tilt axis in the plane. These defects can be considered as point defect lines that are reconstructed with or without dangling ties. 113 , 116 , 117 Defects can also occur at the edges of graphene. These damaged edges can arise due to local changes in the type of reconstruction or due to the continuous removal of carbon atoms from the backbone. 116 , 118

Structural defects greatly affect the chemical and electronic properties of the graphene produced. For the chemical properties of graphene, defects associated with dangling bonds can increase the graphene reactivity. Simulation studies show that every functional group that is perfectly bound to the small binding energy in graphene causes an increase in its reactivity, thus being the reason why its formation must be controlled. 119 , 120

General Synthesis Methods to Produce Graphene

Several methods for producing graphene have been reported. In general, graphene production can be done by two types of methods, which are top-down and bottom-up 84 , 121 , 122 (Fig. 4 ). More information about all methods are discussed as follow:

Figure 4.  Flow-chart of graphene production. 19 , 121 , 123 , 124 , 101

Top-Down Method

The principle of the top-down method is to exfoliate graphite that is used as starting material. 121 , 123 Mechanical exfoliation, chemical/electrochemical exfoliation and chemical/electrochemical fabrications are classified in the top-down methods. The top-down technique is very easy to apply for large-scale graphene production. However, conventional top-down methods, such as Hummer graphite oxidation, requires a controlled reaction and always provide abundant structural defects that cause low electrical conductivity. 89 , 125 , 126 Below are some of the top-down techniques that are usually used by researchers to synthesize graphene:

Exfoliation method

Exfoliation is a simple and common technique that can be used for graphene synthesis from graphite or other carbon sources. There are several types of exfoliation such as mechanical exfoliation, chemical exfoliation and/or electrochemical exfoliation. Mechanical exfoliation or more commonly known as the Scotch tape method, is a traditional method that has been applied for decades. 1 , 21 , 89 This method is made famous by K. Novoselov and Andre Geim since they both won the Nobel Prize in Physics due to the results obtained by implementing this method. Mechanical exfoliation (Fig. 5 a) is the first method to obtain one layer of graphene. 21 , 89 , 127 Examples of mechanical peels are micromechanical peels as shown in Table II . Dasari et al. in 2017 showed a representation of micromechanical stripping of graphene sheets using Scotch tape method. 41 Graphite was placed on the substrate and repeatedly peeled using adhesive tape until a monolayer sheet is obtained. Although this process is simple but the main challenges with this method is that the product that obtained is small and contains some structural defects. 41

Figure 5.  Illustration of mechanical exfoliation (a) and liquid-phase exfoliation (b). Figures were adopted from Novoselov et al., 2012 89 and Dasari et al., 2017. 41

Table II.   Advantage and disadvantage of top-down and bottom-up methods from several studies.

Chemical peel is an effective way to produce large amounts of graphene. However, this method has several disadvantages, such as it involves complex chemical processes and it also generally produces sheet-shaped graphene that has low conductivity. 147 – 149 Liquid phase exfoliation (LPE) is a new top-down method that only involves flaking natural graphite through high-shear mixing or sonication. 21 , 128 , 150 Illustration of liquid phase exfoliation is shown in Fig. 5 b. Until now, there are two different graphite peeling techniques using LPE, and these are cavitation in sonication and high-shear mixing. In practice, the LPE operating conditions are very mild and do not need a vacuum or high temperature system. For large scale applications, the high-shear mixing method or microfluidizer is more recommended than the sonification assisted LPE method. 100 , 151 This is due to the low graphene product and high energy consumption for process with LPE sonication method. Meanwhile, high-shear mixing or microfluidizer method can exfoliate graphite better than the LPE sonication method. 100 , 151 , 152

Electrochemical method

The electrochemical method is carried out using a minimum of four main components, and these are anode, cathode, electrolyte, and power supply (Fig. 6 a). Anode, being a source of carbon, will be oxidized and exfoliated to produce graphene. The cathode can be varied by using either a graphite (Figs. 6 b and 6 c) or a platinum (Fig. 6 d). The experiment is usually arranged as shown in Fig. 6 . The anode and cathode are immersed into the electrolyte at a certain distance. Positive or negative voltage is applied to the anode depending on the desired peeling mechanism. 129 , 153 , 154 The choice of anode, cathode and electrolyte solution used is a crucial factor for the electrochemical process as it can affect the graphene product obtained.

Figure 6.  Electrochemical experiment in generally (a), based on Liu et al., 2013 155 (b), based on Hossain and Wang, 2016 33 and (c), based on Ambrosi and Pumera, 2016 42 (d) to produce graphene.

Liu et al. used a pencil graphite as a source of graphite, which subsequently used it as anode and cathode (Fig. 6 b). 155 The anode and cathode are immersed in 1 M H 3 PO 4 with an applied potential between +7 V and −7 V. The product obtained is not homogeneous, and the thickness and size distribution were quite wide. Parvez et al. in 2013 used graphite as anode and platinum (Pt) as cathode. 156 The electrodes were immersed in sulfuric acid (electrolyte solution) with potential of +10 V for 10 min. The yield of this process was about 60% and the product obtained has 1–3 layers.

Based on the results of the above research, sulfuric acid is an electrolyte suitable for electrochemical intercalation and graphite exfoliation process. The size of the sulfate ions (0.46 nm) which is similar to the graphite interlayer distance (0.335 nm) may contribute to the intercalation process. In addition, electrolysis of sulfate ions and co-intercalated water causes the formation of gases such as SO 2 , O 2 and H 2 . 157 , 158

The use of acid electrolyte caused graphite to be flaking during the intercalation process. This process produce graphene with several layers while the expected product was one layer. 15 , 130 , 159 , 160 , 161 Parvez et al., (2014) proposed a general concept for electrochemical stripping of graphite in inorganic salts as shown in Fig. 7 . 162 Graphite electrodes were immersed in ammonium sulfate solution [(NH 4 ) 2 SO 4 , H 2 O] and applied potential was set to +10 V (Fig. 7 a). At this potential, water reduction occurs at the cathode and produces hydroxyl (OH–) ions as strong nucleophiles. Nucleophiles attack the edges and boundaries of the graphite grains, resulting in oxidation reactions and intercalation of sulfate ions in the graphite layer (Fig. 7 b). Oxidation reactions induce the depolarization and expansion of the graphite layer (Fig. 7 c). During this process, the water molecules act as a co-intercalation with SO 4 2− ions. Oxidized water molecules and SO 4 2− ion reduction produce gas species (SO 2 , O 2 , etc.). Gas species have enough energy to separate the graphite layer and produce layered graphene (Fig. 7 d). The electrolyte concentration at the applied potential also affects the graphite exfoliation process. Parvez et al., reported that the lowest concentration of electrolyte ((NH 4 ) 2 SO 2 ) for the graphite intercalation process was less than 0.01 M to produce 5 wt% graphene. 156 When the concentration was increased in the range of 0.01 to 1.0 M, graphene products will increase to more than 75% by weight. This phenomenon is in accordance with the general mechanism of electrochemical exfoliation of graphite in inorganic salts. 156 , 162

Figure 7.  The mechanism of electrochemical exfoliation proposed by Parvez et al., (2014). 162 Graphite as raw material for synthesis graphene (a), oxidation and intercalation process (b), expansion of graphite layers (c) and product of exfoliated graphene (d).

Graphene can also be synthesized using electrochemical methods in combination with a sonication method. 163 – 167 This combination method can eliminate the use of high temperatures, high pressures, and tiring work steps in the synthesis process. 14 , 129 , 167 – 169 Bai et al., (2017) studied the effect of sonication on disperse graphene stability. 56 Three types of sonication were used, which are bath (200 W, 35 kHz), horn (50 W, 20 kHz) and high-power micro tip (1000 W, 20 kHz). The result shows that horn sonication give the most stable dispersion of the graphene product which is can last up to two years. Meanwhile, the micro-tip sonication requires a higher power intensity that exceeds the optimal energy required, hence this type of sonication fails to produce stable graphene dispersion. Several studies indicate that all sonication techniques are able to produce reduced graphene oxide (RGO). 56 , 165 , 166 , 170 , 171

Bakhshandeh and Shafiekhani, (2018) reported the effects of ultrasonic waves on the graphene properties synthesized by using electrochemical methods. 169 It was found that the ultrasonic waves had a direct effect on graphene production. Ultrasonic waves have the ability to homogenize electrolyte solutions and reduce oxygen groups in graphene structures. The ratio of oxygen groups reduction is proportional to the decrease in defects of the graphene structure. The effect of temperature (25 °C–95 °C) in combination of electrochemical-sonication method for producing graphene also investigated by Hossain and Wang. 33 Characterization using Raman spectroscopy shows the smallest defects in graphene products with increasing temperature. According to the results, in order to obtain the minimum defects, scientists and industries use a high temperature and controlled ultrasonic wave during the synthesis process by electrochemical-sonication combination method.

Laser ablation

Laser ablation is a new method to synthesis nanomaterial, especially graphene. This method has promising advantages, including being environmentally friendly, easy experimental settings (which do not require extreme conditions), long-lasting nanoparticle stability, a free unwanted contaminant in nanoparticle products and avoiding the use of harmful synthesis reactants. 172 – 174 Cappeli et al. in 2015 used the laser ablation to synthesis graphene. Their research was done on silicon (Si) substrates with variations in temperature (from room temperature to 900 °C) using laser Nd:YAG laser operating in the near IR ( λ = 523 nm, repetition rate (ν) = 10 Hz, pulse width ( τ ) = 7 ns, fluence ( φ ) ∼ 7 J cm −2 , deposition time = 15 min). 175 After that, the developing method is carried out with a variety of conditions in order to obtain a high-quality graphene. 35 – 37 , 176

Laser ablation techniques require solid carbon/graphite as a carbon source in order for the laser source to erode the carbon surface and produce graphene. 103 , 177 , 178 Several laser parameters must be controlled during the synthesis process of graphene. 103 This parameter can be adjusted according to the laser ablation system which can affect the product quality. The first parameter that must be controlled is the laser itself, such as fluence laser, wavelength, repetition rate, and pulse duration. The second parameter controlled is the gas background, pressure background, the distance of substrate, substrate temperature. The selection of substrate also influences the product. Koh et al. conducted a feasibility test of various metals as a substrate for graphene synthesis by using the laser ablation method. The metals studied were nickel (Ni), copper (Cu), cobalt (Co) and iron (Fe). 177 The results showed that graphene products have a lattice constant of 0.357; 0.352; 0.361; 0.251 and 0.287 nm when using Ni, Cu, Co and Fe substrates respectively. 179 Hermani et al. obtained a high-quality bilayer graphene using Ni/SiO 2 substrate. 178 This data proved by Raman spectroscopy which shows an improvement of 60% in the results compared to when other substrates are used. The effect of pulses on various substrates has been investigated by Pechlivani et al. in 2017. 180 Ultra-short pulse lasers were used with picosecond lasers for the corresponding wavelengths and pulse energy. The results of this study proved that ultra-short pulse laser technology can be the next generation technology in promoting micro graphene as a valuable material in manufacturing sector. Ultra-short laser ablation was also applied by De Bonis et al. and produced a good graphene product. 181 Generally, the mechanism of graphene synthesis using laser ablation is described as Fig. 8 . The laser source directly hits the carbon/graphite solid and breaks down its structure so that it is released as graphene.

Figure 8.  Mechanism of graphene synthesis by laser ablation.

Bottom-Up Method

Bottom-up method is defined as a deposition strategy of a starting material, carried out under controlled conditions by controlling the variables such as temperature, pressure, flow rate. 121 The bottom-up strategy may produce a high-quality graphene with some structural defects and good electronic properties. However, the amount of graphene produced is relatively small that it is only able to be used for a limited field. Moreover, a defect-free graphene structure with adjusted layers can be produced which can latterly use for special applications. The following are some bottom-up techniques that are usually used for graphene synthesis.

Chemical vapor deposition (CVD)

CVD is one of the most useful methods for synthesizing structural mono or few layer graphene. 9 , 182 A graphene with a large area can be obtained by using CVD by exposing the precursors at a high temperature. The general CVD instrument consists of tube furnace, gas flow, tail gas treatment and substrate as shown in Fig. 9 a. Substrate is a significant material in order for the graphene side to be able to be synthesized. The commonly used substrate is either nickel (Ni) or copper (Cu). Mechanism of the graphene synthesis using CVD method depends on the substrate used (Fig. 9 b). 26 , 41 , 183 , 184 When using Ni substrate, carbon is used as a raw material to produce graphene as it dissolves in Ni at high temperature. The dissolved carbon is separated and precipitated to obtain graphene during the appropriate cooling rate. In contrast, the mechanism of graphene synthesis in Cu substrate by CVD will occur when carbon deposits directly on the surface of Cu substrate. The C/H ratio, substrate quality, temperature, pressure, and oxygen on the substrate surface also affects the process of graphene synthesis when using the CVD method. The optimization process of the size and quality of graphene product by CVD method is usually very difficult due to the numerous interdependent parameters in this method. Papon et al. in 2017 applied a method namely "designs of experiments" to estimate the relative importance and value of the parameters. 185 This design explains interaction of several independent parameters in producing graphene on Cu substrate. The result showed that temperature, time, rate of heating and pre-annealing time of the substrate influence significantly in quality of graphene product. Particularly, there are two main factors for the size of graphene product, i.e., graphene growth time and the increasing rate of the carbon source temperature. It is mean that the researcher just needs modify those factors to change the size dramatically. Furthermore, Liu and Liu in 2017 also stated that a good controlling in synthesis parameters can produce large-area, high quality graphene and large-sized graphene single crystal with different shapes and layers. 186

Figure 9.  CVD device (a) and growth mechanism in CVD process (b). 41

Overall, the CVD method is still one of the successful methods for producing large-scale graphene. The graphene produced using the CVD method is 1.5 times better compared to other methods such as Scotch tape, thermal decomposition, graphene oxide reduction, liquid exfoliation, and even bottom-up method. It is because the graphene single crystal can be produced within 2.5 h when using the CVD method. The graphene single crystal product shows Hall's mobility of 10,000–20,000 cm 2 V 1 S 1 at room temperature. 41 , 104 This property is compatible to be applied in semiconductor technology, solar cells, and transparent conductive films (TCFs). 186

Arc discharge

Arc discharge is a relatively cost-effective and environmentally friendly method for graphene synthesis. 86 , 123 , 147 , 143 Graphene can be produced using the arc discharge method under hydrogen (H 2 ), helium (He), or nitrogen (N 2 ) conditions. 187 , 188 Wu et al. (2010) have developed the arc discharge method to produce few-layered graphene under conditions of He and carbon dioxide (CO 2 ) mixture. 147 The result shows the obtained graphene has fewer defects than graphene produced by chemical methods. The obtained graphene is also able to disperse easily in organic solvents for further applications. The combination of He and CO 2 conditions during the arc discharge process is capable of producing a good graphene for making electrodes in various devices. Another advantage of the graphene produced by using such method is it makes it as a suitable choice for an electric charger used for conducting composite materials.

Kim et al. in 2016 reported a controllable and scalable aqueous arc discharge process that produces high quality bi- and trilayers of graphene. 144 However, they still found by products when using this method, hence a separation method needs to be developed. Development of the arc discharge method to produce graphene was also studied by Cheng et al. in 2018, 23 where they combined a vacuum arc discharge by using CVD method. Graphene was synthesized in a copper foil by using a furnace at a high temperature embedded in a vacuum arc discharge. This merging method can produce a single layer graphene at a high temperature.

Wu et al. explained the mechanism of the arc discharge method to obtain graphene sheets in different atmospheres for large-scale graphene production (Fig. 10 ). 189 Graphene sheets were synthesized using activated carbon as an anode and cathode by arc discharge method under a mixed gases conditions where in this case, nitrogen (N 2 ) and hydrogen (H 2 ) gases were used. The alternating current in the process causes both electrodes to react and evaporate simultaneously, thus eliminating the formation of deposits at the cathode. 143 , 187 , 189 This process increases the temperature, which is needed to increase the diffusion rate of carbon atoms and clusters. The increasing of diffusion rate allows all carbon species and gas molecules to collide between each other. Graphene product can easily be obtained only if hydrogen gas is used since hydrogen gas has a very high cooling rate. To obtain such conditions, Wu et al. combined the hydrogen gas with inert gas such as N 2, which has low thermal conductivity, in order to generate a graphene product with satisfactory quality. 189

Figure 10.  Mechanism of graphene synthesis by arc discharge in Wu et al. (2010). 189

According to the explanation above, the advantages and disadvantages of all methods mentioned above (top-down and bottom-up) are summarized in Table II .

Challenging and Future Outlook for Research and Industry

The advancements in the production strategies have been described, whilst the literatures have been analyzed extensively in evaluating the reinforcement efficiency of each graphene type in a range of matrices by involving different synthesis routes. It should be stated that there are still several challenges to overcome before industries can proceed with the mass production of graphene. An example of the challenges faced is the scale up of the production of high-quality graphene, as this is still a major issue which is always going to be reflected on the ultimate properties of the materials. Based on the findings presented earlier, the best quality graphene to be used in research and industry is the material with the largest aspect ratio with a thickness of few layers. In order for a graphene to be successfully produced graphene, all the parameters should be considered and controlled according to the method or route selected. The product of graphene still needs some characterization, which is compatible to industry scale. The important characterization technique to obtain graphene is Raman spectroscopy, XRD, XPS and other additional characterization for special application such as electrical or surface area parameters.

The different ways of further promoting graphene for mass production is presented in Fig. 11 . It correlates the price of mass production toward the graphene quality obtained using various methods. The best route for graphene synthesis is using a new method, i.e. laser ablation. It opens the possibility of producing a high-quality graphene with the lowest number of defects. This method also is faster than the available method. Simple in procedure and control make this method have the lowest price for mass production which is the important factor in industrial production. Another suitable alternative which may be able to further build on is the electrochemical method. The principle of electrochemical method is to utilize the conductivity of the graphite to intercalate molecules between graphene layers. 129 , 153 , 159 , 163 , 105 Using graphite as an electrode with the presence of electrical energy, intercalation of different charged ionic and facilitating exfoliation is able to be executed. 153 Many researchers have reported that graphene production by electrochemical method exhibits a further possibility of avoiding the use of hazardous chemicals by utilizing electrochemical activation. Electrochemical method may also be applied to obtain a relatively high-quality product with minimum defect and a tunable level of oxidation. Furthermore, electrochemical process also demonstrates the possibility of purifying products in simpler steps when compared to other purifying methods. 153

Figure 11.  Modified flow-chart of graphene production. 89

Acknowledgments

The authors acknowledge to the Indonesian Government, especially the Ministry of Research, Technology, and Higher Education of the Republic of Indonesia (KEMENRISTEKDIKTI) for supporting the research funding of this work under project scheme of Penelitian Disertasi Doktor (PDD) with grant number: T/115/IT2.VII/HK.00.02/XI/2019 and 1244/PKS/ITS/2020. This research is also partially funded by the Indonesian Ministry of Research, Technology and Higher Education under WCU Program, managed by Institut Teknologi Bandung grant number: 1896t/I1.B04.2/SPP/2019.

2013 Theses Doctoral

Graphene NanoElectroMechanical Resonators and Oscillators

Chen, Changyao

Made of only one sheet of carbon atoms, graphene is the thinnest yet strongest material ever exist. Since its discovery in 2004, graphene has attracted tremendous research effort worldwide. Guaranteed by the superior electrical and excellent mechanical properties, graphene is the ideal building block for NanoElectroMechanical Systems (NEMS). In the first parts of the thesis, I will discuss the fabrications and measurements of typical graphene NEMS resonators, including doubly clamped and fully clamped graphene mechanical resonators. I have developed a electrical readout technique by using graphene as frequency mixer, demonstrated resonant frequencies in range from 30 to 200 MHz. Furthermore, I developed the advanced fabrications to achieve local gate structure, which led to the real-time resonant frequency detection under resonant channel transistor (RCT) scheme. Such real-time detection improve the measurement speed by 2 orders of magnitude compared to frequency mixing technique, and is critical for practical applications. Finally, I employed active balanced bridge technique in order to reduce overall electrical parasitics, and demonstrated pure capacitive transduction of graphene NEMS resonators. Characterizations of graphene NEMS resonators properties are followed, including resonant frequency and quality factor ($Q$) tuning with tension, mass and temperatures. A simple continuum mechanics model was constructed to understand the frequency tuning behavior, and it agrees with experimental data extremely well. In the following parts of the thesis, I will discuss the behavior of graphene mechanical resonators in applied magnetic field, {i.e.} in Quantum Hall (QH) regime. The couplings between mechanical motion and electronic band structure turned out to be a direct probe for thermodynamic quantities, {i.e.}, chemical potential and compressibility. For a clean graphene resonators, with quality factors of $1 \times 10^4 $, it underwent resonant frequency oscillations as applied magnetic field increases. The chemical potential of graphene shifts smoothly within each LL, causing the resonant frequency to change in an explicit pattern. Between LLs, the finite compressibility caused the resonant frequency changing dramatically. The overall oscillations of resonant frequency with the applied magnetic field could be fitted with only disorder potential as free parameter. Compared with conventional electronic transport technique, such mechanical measurements proven to be a more direct and powerful tool, which we used o study the properties of graphene's ground states in broken symmetry states. In the last part this thesis, I will present the study of graphene NEMS oscillators with positive feedback loop. The demonstrated oscillators are self-sustained (without external radio frequency, RF, stimulus), and the oscillation frequencies can be controlled by tension{i.e.}, (applied gate voltage). I also carefully studied the influence of feedback gain and phase, as well as linewidth compression as function of temperature.

• Nanotechnology
• Mechanical engineering

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Huang, Xianjun. "Electromagnetic applications of graphene and graphene oxide." Thesis, University of Manchester, 2016. https://www.research.manchester.ac.uk/portal/en/theses/electromagnetic-applications-of-graphene-and-graphene-oxide(873c9618-19a3-4818-b47a-9afbca39857c).html.

Nagar, Bhawna. "Printed Graphene for energy storage and sensing applications." Doctoral thesis, Universitat Autònoma de Barcelona, 2019. http://hdl.handle.net/10803/667240.

Liu, Zhihui. "Properties of 3D Printed Continuous Fiber-Reinforced CNTs and Graphene Filled Nylon 6 Nanocomposites." University of Cincinnati / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1512045511745974.

Vescio, Giovanni. "Inkjet-Printed Flexible Electronic Devices: from High-k Capacitors to h-BN/Graphene Thin Film Transistors." Doctoral thesis, Universitat de Barcelona, 2017. http://hdl.handle.net/10803/406350.

Wilson, Lindsay Robin. "The development of graphene oxide sheet- and polyanilino-immunosensor systems for lipoarabinomannan (LAM) tuberculosis biomarker." University of the Western Cape, 2017. http://hdl.handle.net/11394/5478.

Islam, Md Mazharul. "Printed transparent conducting electrodes based on carbon nanotubes (CNTs), reduced graphene oxide (rGO), and a polymer matrix." Thesis, Umeå universitet, Institutionen för fysik, 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-156366.

Carey, Tian. "Two-dimensional material inks and composites for printed electronics and energy." Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/275609.

Nesser, Hussein. "Fabrication et caractérisation des MEMS composite pour la récupération d'énergie mécanique." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0269/document.

SILVA, Barbara Virginia Mendonca da. "Desenvolvimento de sensores para imunoensaios aplicados ao diagnóstico do infarto agudo do miocárdio." Universidade Federal de Pernambuco, 2016. https://repositorio.ufpe.br/handle/123456789/17770.

Forsberg, Viviane. "Liquid Exfoliation of Molybdenum Disulfide for Inkjet Printing." Licentiate thesis, Mittuniversitetet, Avdelningen för naturvetenskap, 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:miun:diva-29181.

Aqeeli, Mohammed Ali M. "Microwave oscillator with phase noise reduction using nanoscale technology for wireless systems." Thesis, University of Manchester, 2015. https://www.research.manchester.ac.uk/portal/en/theses/microwave-oscillator-with-phase-noise-reduction-using-nanoscale-technology-for-wireless-systems(46287d2a-bc90-4cee-b893-ccf6a3b0747f).html.

De, Kock Izak Jacobus Venter. "The feasibility of the manufacturing of a printed circuit type heat exchanger produced from graphite / Izak Jacobus Venter de Kock." Thesis, North-West University, 2009. http://hdl.handle.net/10394/8312.

Burzynski, Katherine Morris. "Printed Nanocomposite Heat Sinks for High-Power, Flexible Electronics." University of Dayton / OhioLINK, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1619702252056433.

Alabdulwaheed, Abdulhameed. "3D-Printed Fluidic Devices and Incorporated Graphite Electrodes for Electrochemical Immunoassay of Biomarker Proteins." Digital Commons @ East Tennessee State University, 2018. https://dc.etsu.edu/etd/3477.

Alabdulwaheed, Abdulhameed, and Gregory W. Dr Bishop. "3D-Printed Fluidic Devices and Incorporated Graphite Electrodes for Electrochemical Immunoassay of Biomarker Proteins." Digital Commons @ East Tennessee State University, 2018. https://dc.etsu.edu/asrf/2018/schedule/175.

Mazure, David B. "Schema." Digital Commons @ East Tennessee State University, 2009. https://dc.etsu.edu/etd/1812.

Carneiro, Jussara Fernandes. "Eletrocatalisadores para reação de redução do O2 visando a produção eletroquímica de H2O2: síntese e caracterização de óxidos metálicos nanoestruturados (Ta2O5, MoO3, Nb2O5 ou ZrO2) incorporados em carbono Printex 6L e em grafeno." Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-13012016-092200/.

Costa, Guilherme Cadete Paixão da. "3D Printed Graphene Based Supercapacitors." Master's thesis, 2019. http://hdl.handle.net/10362/92312.

Machado, Mónica Isabel de Abreu. "Laser induced/scribed graphene electrodes for all printed transistors." Master's thesis, 2017. http://hdl.handle.net/10362/118783.

"3D Printed Glucose Monitoring Sensor." Master's thesis, 2017. http://hdl.handle.net/2286/R.I.44220.

Chou, Meng-Chuin, and 周孟群. "A Inkjet Printed Piezoresistive Graphene Tactile Sensor For Endosurgical Palpation Applications." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/09122865076545115533.

Hsu, Ting Kang, and 許庭綱. "Investigation of graphene-nanoparticle nanocomposites and graphene nanoribbons on screen-printed electrodes using flow injection system for biosensor applications." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/14782044696173773535.

Lee, Ming-Che, and 李明哲. "Determination of uric acid using screen-printed electrode modified with ATT and graphene oxide." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/9es9j5.

Chang, Chia Wei, and 張家瑋. "Investigation of graphene/nickel oxide-modified screen-printed carbon electrodes for nonenzymatic glucose sensor applications." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/57517277026715029315.

Cheng-HuiChen and 陳正慧. "Reduced Graphene Oxide and Diamine Oxidase Immobilized Screen-Printed Carbon Electrode for Histamine Detection in Food." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/98392494761656160000.

Chang, Shuo-Wen, and 張碩文. "Graphene Oxide Synthesis by Electrochemical Exfoliation and Its Application for Microvia Plating of a Printed Circuit Board." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/h5g864.

SU, JIAN-WEI, and 蘇建維. "Graphene-Poly(2,5-Diamino-Benzenesulfonic Acid)-Composite Materials-Modified Screen-Printed Carbon Electrodes for Electrochemical Analysis of Uric Acid." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/m54547.

SHEN, PEI-WUN, and 沈姵妏. "Nitride graphite / manganese dioxide screen-printed carbon electrode nitrite detection and the detection of 4-hydroxynitrobenzene in river water by nickel disulfide/graphene oxide glassy carbon electrode." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/8e94qg.

Lee, Chia-Ming, and 李家銘. "Green synthesis of gold nanoparticle/graphene oxide and electrochemically activated screen printed carbon Ni nanoparticles modified electrodes for electrocatalysis and antimicrobial activity." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/n8t5r2.

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Prize-Winning Thesis and Dissertation Examples

Published on September 9, 2022 by Tegan George . Revised on July 18, 2023.

It can be difficult to know where to start when writing your thesis or dissertation . One way to come up with some ideas or maybe even combat writer’s block is to check out previous work done by other students on a similar thesis or dissertation topic to yours.

This article collects a list of undergraduate, master’s, and PhD theses and dissertations that have won prizes for their high-quality research.

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Award-winning undergraduate theses, award-winning master’s theses, award-winning ph.d. dissertations, other interesting articles.

University : University of Pennsylvania Faculty : History Author : Suchait Kahlon Award : 2021 Hilary Conroy Prize for Best Honors Thesis in World History Title : “Abolition, Africans, and Abstraction: the Influence of the “Noble Savage” on British and French Antislavery Thought, 1787-1807”

University : Columbia University Faculty : History Author : Julien Saint Reiman Award : 2018 Charles A. Beard Senior Thesis Prize Title : “A Starving Man Helping Another Starving Man”: UNRRA, India, and the Genesis of Global Relief, 1943-1947

University: University College London Faculty: Geography Author: Anna Knowles-Smith Award:  2017 Royal Geographical Society Undergraduate Dissertation Prize Title:  Refugees and theatre: an exploration of the basis of self-representation

University: University of Washington Faculty:  Computer Science & Engineering Author: Nick J. Martindell Award: 2014 Best Senior Thesis Award Title:  DCDN: Distributed content delivery for the modern web

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University:  University of Edinburgh Faculty:  Informatics Author:  Christopher Sipola Award:  2018 Social Responsibility & Sustainability Dissertation Prize Title:  Summarizing electricity usage with a neural network

University:  University of Ottawa Faculty:  Education Author:  Matthew Brillinger Award:  2017 Commission on Graduate Studies in the Humanities Prize Title:  Educational Park Planning in Berkeley, California, 1965-1968

University:  University of Ottawa Faculty: Social Sciences Author:  Heather Martin Award:  2015 Joseph De Koninck Prize Title:  An Analysis of Sexual Assault Support Services for Women who have a Developmental Disability

University : University of Ottawa Faculty : Physics Author : Guillaume Thekkadath Award : 2017 Commission on Graduate Studies in the Sciences Prize Title : Joint measurements of complementary properties of quantum systems

University:  London School of Economics Faculty: International Development Author: Lajos Kossuth Award:  2016 Winner of the Prize for Best Overall Performance Title:  Shiny Happy People: A study of the effects income relative to a reference group exerts on life satisfaction

University : Stanford University Faculty : English Author : Nathan Wainstein Award : 2021 Alden Prize Title : “Unformed Art: Bad Writing in the Modernist Novel”

University : University of Massachusetts at Amherst Faculty : Molecular and Cellular Biology Author : Nils Pilotte Award : 2021 Byron Prize for Best Ph.D. Dissertation Title : “Improved Molecular Diagnostics for Soil-Transmitted Molecular Diagnostics for Soil-Transmitted Helminths”

University:  Utrecht University Faculty:  Linguistics Author:  Hans Rutger Bosker Award: 2014 AVT/Anéla Dissertation Prize Title:  The processing and evaluation of fluency in native and non-native speech

University: California Institute of Technology Faculty: Physics Author: Michael P. Mendenhall Award: 2015 Dissertation Award in Nuclear Physics Title: Measurement of the neutron beta decay asymmetry using ultracold neutrons

University:  Stanford University Faculty: Management Science and Engineering Author:  Shayan O. Gharan Award:  Doctoral Dissertation Award 2013 Title:   New Rounding Techniques for the Design and Analysis of Approximation Algorithms

University: University of Minnesota Faculty: Chemical Engineering Author: Eric A. Vandre Award:  2014 Andreas Acrivos Dissertation Award in Fluid Dynamics Title: Onset of Dynamics Wetting Failure: The Mechanics of High-speed Fluid Displacement

University: Erasmus University Rotterdam Faculty: Marketing Author: Ezgi Akpinar Award: McKinsey Marketing Dissertation Award 2014 Title: Consumer Information Sharing: Understanding Psychological Drivers of Social Transmission

University: University of Washington Faculty: Computer Science & Engineering Author: Keith N. Snavely Award:  2009 Doctoral Dissertation Award Title: Scene Reconstruction and Visualization from Internet Photo Collections

University:  University of Ottawa Faculty:  Social Work Author:  Susannah Taylor Award: 2018 Joseph De Koninck Prize Title:  Effacing and Obscuring Autonomy: the Effects of Structural Violence on the Transition to Adulthood of Street Involved Youth

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Graphene Properties, Synthesis and Applications: A Review

Akanksha r. urade.

1 Centre of Excellence: Nanotechnology, Indian Institute of Technology Roorkee, Roorkee, 247667 India

Indranil Lahiri

2 Department of Metallurgical and Materials Engineering, Indian Institute of Technology Roorkee, Roorkee, 247667 India

K. S. Suresh

We have evaluated some of the most recent breakthroughs in the synthesis and applications of graphene and graphene-based nanomaterials. This review includes three major categories. The first section consists of an overview of the structure and properties, including thermal, optical, and electrical transport. Recent developments in the synthesis techniques are elaborated in the second section. A number of top–down strategies for the synthesis of graphene, including exfoliation and chemical reduction of graphene oxide, are discussed. A few bottom–up synthesis methods for graphene are also covered, including thermal chemical vapor deposition, plasma-enhanced chemical vapor deposition, thermal decomposition of silicon, unzipping of carbon nanotubes, and others. The final section provides the recent innovations in graphene applications and the commercial availability of graphene-based devices.

Introduction

In 2004, Geim et al. synthesized a stable monolayer of graphene through mechanical stripping. Geim and Novoselov were awarded the Nobel Prize in Physics in 2010 for their successful experiments, and, subsequently, graphene became one of the world's most studied two-dimensional materials. 1 Graphene is a single atomic layer of carbon atoms arranged in a hexagonal pattern. It has a thickness of only 0.334 nm, making it the world's thinnest material. It has numerous distinguishing qualities due to its unique properties, such as a large specific surface area (~ 2600 m 2 /g), 1 high electron mobility (200,000 cm 2 /Vs), 2 enhanced thermal conductivity (3000–5000 Wm/K), 3 extreme optical transparency (97.4%), 4 and exceptional mechanical strength, with a Young’s modulus of 1 TPa. 5

An experimental demonstration of the thermal chemical vapor deposition (CVD) method for synthesizing a few-layer nano-graphene with roughly 35 layers of graphene was made 2 years after the first report on graphene synthesis. 6 To create a large-area graphitic film with three to six graphene layers, Obraztsov et al. resorted to the CVD approach. 7 Eda et al. produced large-area (10 cm 2 ) reduced graphene oxide (rGO) film using the vacuum infiltration method. 8 In 2009, Li et al. used the CVD approach to successfully create high-quality, large-area uniform graphene sheets on copper substrates. 9 In their study, more than 95% of the 1-cm 2 film was monolayer graphene, 3–4% was bilayer graphene (BLG), and the remaining 1% was few-layer graphene (FLG). They discovered that graphene formed on copper via a surface-catalyzed mechanism. They also demonstrated graphene synthesis on a quartz substrate with an improved approach for transferring graphene to other substrates with minimum defects. Bae et al. reported the first roll-to-roll (R2R) method for producing large-`area 30-inch (c. 760 mm) diagonal films utilizing CVD on flexible ultra-large copper substrates. 10 With the R2R approach, the films can be transferred directly onto the desired substrate. Paton et al. synthesized graphene nanoplatelets (GNP) from graphite by liquid phase exfoliations (LPE) in 2014. 11 The GNPs produced by LPE have a limited lateral dimension of a few micrometers, and can range in thickness from monolayer to more than ten layers. Later, Luong et al. established flash Joule heating as a quick, effective, and scalable method to produce graphene in a few grams from a range of feedstocks, including waste food, plastics, coal, carbon black, and petroleum coke. 12 This was the breakthrough research in the direction of graphene commercialization. The technique employs a "flash" of electricity to heat the carbon to approximately 3000 K, converting it into graphene flakes.

Graphene’s high electron mobility makes it an ideal material for semiconductor device applications requiring fast response times. 13 , 14 The high conductivity of graphene combined with high optical transparency has attracted applications such as a transparent conductive layer for photonic devices. 15 In addition to these, graphene holds a great deal of promise for other areas, such as anticorrosion coatings 16 and paints, 17 sensors, 17 wearable and flexible displays, 18 solar panels, 19 faster DNA sequencing, 20 drug delivery, 21 etc. Most of these applications require high-quality SLG or BLG. The last few years have seen much progress in the controllable synthesis and large-scale synthesis of graphene by mechanical exfoliation 22 or chemical exfoliation, 23 as well as CVD. 24 , 25 The production methods and subsequent processing techniques mostly decide the morphology and structure of the graphene, and also govern the potential applications. Therefore, Sect.  2 reports on the structure and properties, while Sect.  3 covers synthesis techniques, followed by a detailed discussion of its potential applications.

Structure and Properties of Graphene

The number of layers of graphene regulates the different properties. SLG and BLG are zero band gap semiconductors owing to the encounter of the conduction and the valance bands at the Dirac points. 26 A band gap can be opened in BLG by the application of an electric field. 27 Furthermore, for FLG, the structure becomes more metallic with increasing layers. 28 Hence, to comprehend the application of graphene, it is crucial to first understand the graphene properties. This section will review the structure and properties of graphene.

Structure of Graphene

SLG is a sp 2 hybridized structure with two carbon atoms in a unit cell, and these two carbon atoms are located in the A and B positions, respectively (Fig.  1 a). 29 BLG can be divided primarily into three categories: AA-stacked, AB-stacked, and twisted 29 , 30 (Fig.  1 b). On the other hand, tri-layer graphene (TLG) has three stacking options. The AAA, ABA, and ABC stacking sequences represent the hexagonal, Bernal, and rhombohedral arrangements, respectively 31 (Fig.  1 c). Three out of four valence electrons for each carbon atom in graphene's honeycomb lattice overlap with the adjacent carbon atom within the sheet, forming a strong sigma bond. The exceptional flexibility and robustness of graphene's lattice structure are due to the sigma bond. The remaining fourth electron in the Pz orbital overlaps with the neighboring orbitals and forms a π bond that regulates the interaction between the graphene layers (Fig.  1 d).

(a) SLG structure, A and B denote carbon sites, (b) BLG stacking types, (c) TLG stacking types, (d) π bond and sigma bond positions in the graphene honeycomb lattice.

Properties of Graphene

Two linear bands in the band structure of the SLG cross at the Fermi level in the first Brillouin zone, which are Dirac points. Graphene is thus a zero-gap semiconductor (Fig.  2 a). 27 Holes and electrons near the Dirac point behave as massless fermions (m* = 0) and travel at extremely high speeds (10 6  m/s). SLG is recognized as a crucial material for electronics devices due to its outstanding properties and high flexibility. However, the zero-gap constrains its applications. Hence, the first obstacle to overcome is the opening of a gap. A perpendicular electric field applied across the graphene layer tunes the band gap of BLG and TLG due to different stacking sequences. 30 , 31 Oostinga et al. demonstrated the change in carrier mobility from ∼ 1,000 cm 2 /Vs to ∼ 3,000 cm 2  /Vs by tuning the gate voltage 27 (Fig.  2 b–c).

Band structure of (a) SLG, (b) BLG without an electric field, and (c) BLG with perpendicular electric field (reprinted with permission from Ref. 27 ), (d) ABA and ABC stacked TLGs under an electric field (reprinted with permission from Ref. 32 ), (e) band structure of ABAB stacked FLGs under an electric field (reprinted with permission from Ref. 33 ), (f) thermal conductivity of FLG observed as a function of the number of atomic planes (reprinted with permission from Ref. 34 ), (g) imaginary part of graphene's dielectric function as it has evolved at various growth temperatures (reprinted with permission from Ref. 35 ).

In the low-energy region, Bernal TLG has two parabolic bands and one pair of linear bands, as shown in Fig.  2 d. 32 When the electric field exceeds 1 V/nm, the top of the valence band exceeds the bottom of the conduction band, and the band gap disappears. The energy gap of Bernal BLG varies monotonically with the electric field. Thus, Bernal TLG behaves like a semimetal in the perpendicular electric field. Near the K point, there are three pairs of parabolic bands for the rhombohedral TLG. When the perpendicular electric field is continuously increased, the energy gap for initially increases and then decreases. Bernal and rhombohedral TLG have different electronic properties due to stacking sequences.

FLG’s electronic structure is extremely sensitive to thickness, becoming increasingly metallic with increasing layers. Tang et al. investigated the effects of an electric field on FLG with layer numbers greater than 4. 33 An external electric field can convert all ABC stacking graphene with N > 4 to semiconductors, whereas ABA stacking graphene remains semi-metallic (Fig.  2 e).

In addition to its distinctive electrical properties, graphene has a very high thermal conductivity. At ambient temperature, the intrinsic thermal conductivity of single-layer suspended graphene is in the range of 4800–5300 W/mK 4 . In comparison, high-quality graphite has a thermal conductivity of only 2000 W/mK. Suspended graphene from CVD has a thermal conductivity that ranges from 1500 to 5000 W/mK at room temperature (RT). 36 A number of independent experimental reports have validated graphene's high thermal conductivity values. 37 – 40 The thermal conductivity of supported graphene at RT is 600 W/mK and is lower than that of suspended graphene due to phonon scattering at the defects site and thermal coupling to the substrate. 41 Graphene flake thermal conductivity changes with size, and that heat is transferred mainly by acoustic phonons. For instance, the thermal conductivity of suspended FLG initially reduces with an increasing number of layers, then recovers and reaches the bulk graphite limit of 2000 W/mK (Fig.  2 f). 34 The intrinsic features defined by phonon–phonon scattering help to address the interdependence of thermal conductivities on the number of graphene layers. As the number of graphene layers increases, the phonon dispersion changes, resulting in more phonon states available for Umklapp scattering. The greater the Umklapp scattering, the lower the inherent thermal conductivity.

Graphene's unique optical feature can be attributed to its distinctive two-dimensional band structure. 42 It has been shown from the linear optical characterization that graphene absorbs approximately 2.3% of the incident red light and 2.6% of the green light. 43 However, the relationship is linear, and each layer absorbs 2.3% of light. This means that a graphene sample with 5 layers would absorb 11.5% of light and be about 88% transparent. 44 In addition, graphene absorbs over a wide spectral range, from the visible to the infrared region. 45 Interband transitions could explain the light absorption from the visible to the near-infrared range. On the other hand, intraband transitions or free carrier absorption are responsible for the optical response in the far infrared range. As graphene lacks definite energy band levels, it can absorb the radiation regardless of its frequency. Graphene may also produce optical transitions in electric fields, known as gate-dependent optical transitions. 46 The low density of states at the Dirac point causes the Fermi level of graphene to change in the presence of an applied electrical field. This property is useful in electronics to modulate the current, because a change in the Fermi level modifies conductivity, as well as tunes the transmission of an optical source. Ni et al. obtained the refractive index ( n ) of monolayer graphene grown on a 285-nm-thick Si substrate as  n  = 2.0 − 1.1 i  in the visible spectrum, slightly different from that of bulk graphite, n G  = 2.6 − 1.3 i . 47 The refractive index of graphene on such substrates depends on the wavelength and the incident angle of the illumination. By fitting to experimental spectra as a function of wavelength, the complex refractive index of graphene and graphite may be generally represented as n  = 3 −  iC /(3 λ ) (where λ is wavelength and C  = 5.446 μm −1 ). 48 Ochoa-Martínez et al. reported the refractive index of monolayer graphene as ~ 4 and for bilayer graphene as ~ 3.5. 49 A dielectric function is the sum of real and imaginary dielectric functions. 50 The graph between imaginary dielectric function and critical point (CP) transition energy is used to deduce the thickness dependence of the graphene on dielectric function. Bouhafs et al. reported that the dielectric function of graphene increases as the number of graphene layers grows, or as the temperature of graphene growth increases (Fig.  2 g). 35 While graphene synthesized at 2000°C exhibits a dielectric function comparable to that of graphite, graphene formed at 1800°C exhibits graphene-like characteristics. The CP transition energy in the dielectric function of graphene is red-shifted with increasing thickness (or temperature), which is accompanied by an increase in polarizability, as shown in Fig.  2 . Exceptionally higher mechanical properties of graphene have been assessed using an atomic force microscope, and the intrinsic breaking strength and elasticity of free-standing monolayer graphene are reported as 130 GPa and 1 TPa, respectively 51 , 52 Table ​ TableI I shows the comparison between some properties of SLG, BLG, FLG, GO, and rGO.

Comparison between some properties of SLG, BLG, FLG, GO, and rGO

Recent Advances in Graphene Synthesis Techniques

Ruoff et al. 75 separated the graphene layer from the graphite flakes using adhesive tape. Following exfoliation, these layers were dry-deposited on a silicon wafer, referred to as the 'Scotch tape' method. Later, Novoselov and co-workers successfully synthesized a high-quality monolayer graphene by the Scotch tape method. 76 Achieving high-quality graphene on a mass scale is one of the limiting issues to realizing its wide applications. The graphene synthesis techniques have been broadly classified in the following sections.

Exfoliation of Graphite

Even though the quality of graphene produced by Scotch tape or micromechanical cleavage is excellent, 76 , 77 the yield is low, and the process is time-consuming. As a result, this method is limited to laboratory research and appears impractical for industrial production. 78 To improve the efficiency, Jayasena et al. reported a different mechanical cleavage approach for producing FLG from bulk graphite. 79 The technique exfoliates graphite with an ultra-sharp single-crystal diamond wedge, followed by ultrasonic oscillations. Narayan et al. obtained about 30% yield of SLG and FLG sheets with only a few defects by directly sonicating graphite flakes in an aromatic semiconducting surfactant perylene tetracarboxylate (PTCA). 80 They also observed that dried graphene/PTCA powders are easily re-dispersible in water.

Kaplan's group used silk nanofibers as a surfactant during shear mixing in a kitchen blender. 81 They achieved graphene dispersion with > 30% yield of FLG with a production rate greater than 6 g/h. Xu et al. achieved production rates of up to 25 g/h for FLG (70% of that being 1–3 layers), with high conductivity and very low defect density, using electrochemically-assisted exfoliation. 82 Keshri et al. reported chemical- and solvent-free graphite exfoliation using plasma spraying. Most notably, without using a solvent, synthesis rates of up to 48 g/h have been documented, and a material cost of US$1.12 g −1 has been predicted with batch-to-batch repeatability 83 (Fig.  3 ).

(a) Graphite plasma spray exfoliation, (b) TEM images of SLG and BLG, (c–e) Raman spectra of the synthesized graphene, the basal plane and the edge of graphene flakes, (f) distribution of the thickness of graphene flakes (reprinted with permission from Ref. 83 ).

Chemical Oxidation and Reduction Method

One of the traditional techniques for producing large amounts of graphene is the chemical reduction of GO. Initially, GO is produced via graphite oxidation using the modified Hummers method. 84 Then, the prepared GO is reduced by hydrazine 85 and sodium borohydride. 86 The chemical reducing agents like hydrazine are not environmentally friendly and create hazardous by-products. 87 Hence, researchers started to find safe and environmentally friendly reducing agents. 88

Abdolhosseinzadeh et al. reported fully scalable graphene mass production by reducing graphite oxide with ascorbic acid. 89 A different approach is with plant-based extracts being used as a reducing agent, as these are non-hazardous, comparatively cheap, and easily available in the market. Upadhyay et al. used grape extract as an alternative to the conventional toxic reducing agents. 90 Mahata et al. have used Tulsi leaf as a green alternative for bio-reduction of GO with 90% yield. 91 In a recent review, Park et al. reported detailed information about the chemical methods for graphene production. 92

Thermal Chemical Vapor Deposition (CVD)

In the CVD method, gas species are brought into the reactor, where they travel through the hot zone. At the surface of the metal substrate, hydrocarbon precursors break down into carbon radicals. These carbon radicals then self-assemble to form the graphene layer. In the course of the reaction, the metal substrate acts as a catalyst and affects the quality of graphene. In recent years, a variety of transition metals, such as Ru, 93 Ir, 94 Pt, 95 , 96 Co, 97 Pd, 98 Ni, 99 and Cu, 100 – 102 have been used as a catalyst.

The solubility of carbon in Cu is 0.04% at 1000°C. 103 The graphene growth happens via surface adsorption in Cu due to low solubility, while surface segregation/precipitation is the main mechanism in metals such as Ni having higher solubility. Therefore, it is easier to obtain a monolayer graphene on a Cu substrate. Wood et al. reported growing mono- to few-layer graphene on polycrystalline Cu at 1000°C using methane (CH 4 ). The crystal quality and the orientation of the Cu substrate greatly influenced the quality of the graphene growth. After CVD, Raman spectroscopy shows that the (111) having facets produce pristine monolayer graphene while Cu (100) surface prefers multilayer graphene growth. Epitaxial growth of large-area graphene on a (111)-oriented Cu single crystal is possible via CVD. 102 Ishihara et al. reported the synthesis of SLG on Cu (111), and found that the Cu(111) is the optimal surface for defect-free graphene growth. 101

The solubility of carbon in Ni is 2.03% at 1000°C and decreases with temperature. Since the formation of graphene on Ni is carbon segregation and precipitation, different cooling rates produce distinct segregation behaviors, affecting the thickness and the quality of the graphene films. 104 The atomically smooth surface in the single-crystal substrate enabled the preferential growth of monolayer/bilayer graphene, while, in a polycrystalline Ni substrate, multilayers were obtained. 105

Some of the major defects include wrinkles, folds, vacancies, line defects, adatoms, and impurities, all of which degrade graphene's performance for efficient applications. To overcome this issue, Ruoff et al. reported the synthesis of fold-free single-crystal graphene film on Cu-Ni(111) with dimensions of 4 cm × 7 cm 106 (Fig.  4 a, b). Bae et al. reported CVD growth of monolayer graphene on large flexible Cu foils with dimensions as large as 30 inches (c. 760 mm) diagonally, which was then transferred to the target using the R2R method. 107 The graphene sheet resistance was as low as ~ 125 Ω/sq with 97.4% optical transmittance.

(a) CVD furnace system, (b) Raman spectra and mapping of the produced graphene (reprinted with permission from Ref. 106 ), (c) roll-to-roll CVD apparatus, (d) Raman spectra, and (e) transmittance of the transferred graphene film (reprinted with permission from Ref. 108 ).

Plasma Chemical Vapor Deposition

The approaches to growing high-quality graphene films on transition metal substrates are dominated by high-temperature thermal CVD. A low-temperature process for graphene synthesis would be required for applications in electronic devices, and plasma CVD could be an excellent alternative to thermal CVD. The formation of plasma from the reacting gas precursors enables thermal CVD deposition at a lower temperature. 109 Kim et al. decreased the synthesis temperature to 450 °C and reported graphene on Ni foil with the high transparency of 89%. 110 Yamada et al. used microwave plasma CVD to create 294-mm-wide FLG films on a Cu substrate at 400°C with 95% optical transmittance (Fig.  4 c, d). 108 With the lowest synthesis temperature of 317°C, graphene layers having optical transmittance in the range 78–94% have been achieved. 111

Thermal Decomposition of Silicon Carbide (SiC)

Although the CVD technique has emerged as a promising method for producing large-scale graphene, the graphene layer must be transferred onto a suitable substrate for further application. In this context, thermal SiC decomposition eliminates the need for graphene transfer for synthesizing electronic devices. 112 Since the carbon vapor pressure is insignificant in comparison to that of silicon, when heated for a short period of time (1–20 min), the Si atoms desorb and leave behind the carbon atoms, which then rearrange to form graphitic layers. 113 , 114 Emtsev et al. have demonstrated the synthesis of large-area monolayer graphene films on SiC at normal atmospheric pressure and 1650°C. 115 The presence of argon reduces the rate of Si evaporation, resulting in a substantial enhancement in graphene surface morphology on the SiC. 116 It is also possible to synthesize wafer-scale graphene films (mm scale) at a significantly lower temperature (1100°C) on a Ni-Cu-coated SiC substrate. 117

Un-zipping CNTs and Other Methods

One of the most recent techniques for producing graphene involves un-zipping of carbon nanotubes (CNT) to produce graphene nanoribbons (GNRs) in a controlled way with precise dimensions. The multiwall carbon nanotubes (MWCNTs) were unzipped by various experimental methods, such as using a mixture of acids, 118 a catalytic cutting method, 119 electric zipping, 120 and H-based unzipping, 121 etc. CNTs were utilized as the starting material for the catalytic cutting method. Carbon atoms in CNTs diffuse on the metal nanoparticles at ~ 900°C under an argon–hydrogen environment. Following that, the particles become saturated and react with H 2 . The cutting can be driven in one of the two directions, depending on the particle size, resulting in the armchair or zigzag edges. Elias et al. reported using Ni or Co to longitudinally cut and open MWCNTs to create graphitic nanoribbons, typically 100–500 nm long and 15–40 nm wide. 122

Similarly, Wang et al. reported the top–down synthesis of GNRs using oxidative splitting with (NH 4 ) 2 S 2 O 8 in anhydrous acidic media. 123 This method produces GNRs with a high proportion of oxygen functionalities, which alters their properties. Kumar et al. probably addressed this issue by irradiating MWCNTs with a laser pulse energy of 200–350 mJ. They demonstrated that their laser irradiation method is a simple way to produce GNRs with no surface contamination. Although CNT unzipping and subsequent trimming can effectively reduce the width of the GNR, the unzipping process has a low yield. 124

In another recent approach, Su et al. documented the synthesis of template-free nitrogen and sulfur co-doped 3D graphene networks (3DGNs) using the hydrothermal method. 125 Other than the hydrothermal method, the sugar-blowing method is currently the most fascinating and inexpensive technique for growing 3DGNs. Synthesis of a 3D graphene bubble network using the sugar-blowing approach following a polymeric predecessor was proposed by Wang et al. 126 Glucose is mixed with an ammonium salt and treated at 1350°C for 3 h under an Ar environment. A black foam-like, 3D self-supported graphene product was collected. Very recently, Han et al. also reported a sugar-blowing-assisted thermal reduction of GO to produce high-quality 3D porous graphene (3D-PG). 127 By adjusting the synthesis conditions, the microstructure and properties of the 3DGNs can control. For example, the pore size and porosity of 3D-PG can be tuned by changing the metal templates' pore structure in template-assisted CVD. Table ​ TableII II shows the comparison between the synthesis method, product, basic properties, and application of graphene.

Comparison between synthesis method, product, basic properties, and application

Applications of Graphene

Transistors and transparent display.

The use of graphene in field-effect transistors (FET) is one of the promising applications of this material. Since graphene is a conductive material, it cannot be utilized directly in transistor applications. However, graphene in the form of nanoribbons acts as a semiconductor. This means that it can exhibit a band gap and can be turned on and off; thus, can be a crucial component of nanotransistors. 143 By patterning graphene into GNRs, the band gap can be engineered to have values up to 400 meV. 144 There are various methods for fabricating GNRs for FET applications, including chemical and lithographic methods. GNRs with widths ranging from 20 to 30 nm have been created using lithographic patterning. However, a recent study by Llinas et al. reported the fabrication of GNRs of only 0.95 nm in width and with a high current on/off ratio ~ 10 5  at RT (Fig.  5 a, b). 145 Wu et al. reported the synthesis of a side-wall transistor with the smallest gate length of 0.34 nm and up to 1.02 × 10 5 on/off ratios. 140 The side-wall transistors were fabricated using CVD with graphene and molybdenum disulfide (MoS 2 ) to achieve devices below 1 nm. The mobility of graphene FET depends on the choice of substrate materials. In this context, Alam et al. created a graphene-based ferroelectric FET having a mobility ~ 4.2 × 10 4  cm 2 /Vs, and about a 10 3 on/off ratio. 146

(a, b) STM image of synthesized GNR on Au and a schematic of a graphene nanoribbon FET (reprinted with permission from Ref. 145 ), (c, d) device configuration of graphene transparent conducting electrode and optical transmittance comparison between indium tin oxide (ITO) and graphene (reprinted with permission from Ref. 130 ).

Indium tin oxide (ITO) is a transparent conducting material used in smartphones, television screens, and many touchscreen applications. However, the limited availability of indium is a growing concern in the ITO market. It is anticipated that graphene will be one of the materials that will be in the highest demand for the development of future optoelectronic devices. Gautam et al. reported 85–95% transmittance with the sheet resistance in the range of 50–350 Ω/sq for monolayer graphene to F:G. 147 Graphene-based organic light-emitting diodes fabricated directly on a transparent sapphire substrate using metal–organic chemical vapor deposition (MOCVD) is expected to have fewer defects. 130 Figure  5 b, c demonstrates the schematic and optical transmittance of > 97% from the visible to the near-infrared region identical to conventional ITO anodes.

Silver films are extensively utilized as optical coatings; however, silver is expensive, unstable in air, and prone to oxidation, although common protective coatings have the ability to stop corrosion of silver, but change the optical properties. When compared to bare silver, the rate of corrosion of silver films covered with graphene was reduced by 66 times. 148 Prasai et al. 149 found that the graphene-covered copper exhibited a corrosion rate 7 times lower than that of bare copper in sodium sulfate solution. Similarly, in the case of Ni covered with graphene, an enhancement in the corrosion resistance by 20 times was obtained.

Graphene and its derivatives are also widely used as reinforcements in coatings to improve wear resistance. 150 The titanium alloy matrix has a relative wear resistance of 1 and, with an optimum graphene content of 3 g/L the resistance is increased to 12.2. Graphene-modified Al 2 O 3 /TiO 2 coatings have a 20–25% lower wear rate than non-graphene coatings. 151 Zuo et al. 152 also observed an improvement in the wear resistance of a micro-arc oxidation (MAO) coating prepared on Ti-6Al-4 V alloy with GO. They found that the MAO coating with 10 mL/L GO had comparatively superior tribo-corrosion resistance, with fewer microcracks but a smoother worn surface than that of 5- and 15-mL/L GO coatings (Fig.  6 a).

(a) SEM micrographs of wear scars after tribo-corrosion experiments (G0: no GO, G1: 5 ml/l, G2: 10 ml/l, G3: 15 ml/l) (reprinted with permission from Ref. 152 ), (b) before and after oxidation images of bare and rG-O-coated Cu foils (reprinted with permission from Ref. 153 ), (c) field trial images of (A–C) virgin silicone fouling release coating formulation and (D–F) PDMS/GO-Al2O3 coating formulation after 90 days in natural marine water (reprinted with permission from Ref. 154 ).

Graphene coatings can act as a high-energy barrier in the path of oxygen atoms. 155 Kang et al. 153 observed an enhancement in the oxidation resistance of Fe and Cu foils coated with rGO multilayers (Fig.  6 b). Chen et al. reported similar findings, demonstrating that Cu and Si metal surfaces, when coated with graphene, are well shielded from oxidation even after being heated to 200°C for up to 4 h. 156

Superhydrophobic surfaces fabricated from graphene exhibit an excellent anticorrosion property. 154 A recent study by Miler et al. holds exciting potential for creating water-repellent coatings using gas-phase synthesized graphene, with a water contact angle of 153° ± 3°. 137 The graphene grown by their reported method immediately can repel water without any chemical modifications. In another study, the use of the matrix material PDMS and rGO produced a robust superhydrophobic surface with a water contact angle of 159° ± 2°, which had self-cleaning, antifouling, and anticorrosion properties, indicating its potential applications in the marine industry 154 (Fig.  6 c).

Healthcare and Medicine

The biocompatibility of graphene derivatives allows their substantial use in medicine and biology. One of the foremost critical applications is in the early diagnosis of viruses. For example, Miranda et al. developed a graphene-based electrical biosensor for the early detection of malaria parasites (Fig.  7 a, b). 157 In this study, an rGO-based field-effect transistor (2DBioFET) was biofunctionalized with molecules that selectively bind to a malaria biomarker, i.e., Plasmodium falciparum lactate dehydrogenase (PfLDH), with a detection limit down to 0.11 pg/mL. Similarly, Walters et al. developed a graphene sensor platform for rapidly diagnosing the hepatitis virus, 158 and reported a detection limit down to 100 pg/mL in less than 4 min, even with smaller volume samples, i.e., 5 μL. The sensor is easily adaptable to other infectious disease markers, such as hepatitis B virus, SARS-CoV-2, HIV, and many others. Roslon et al. developed a graphene drum to assess rapid antibiotic susceptibility to bacteria in drug screening. 159 A silicon chip containing thousands of these graphene-covered cavities was placed inside an E. coli -containing cuvette. The nanomotion of E. coli bacterium caused the suspended graphene membrane to deflect, as detected by laser interferometry, and then be converted into a soundtrack. The nano-motion of bacterium rapidly decreases in the presence of antibiotics unless the bacteria are resistant to the antibiotic.

(a) The 2DBioFET, (b) the results of PfLDH detection in human serum by the 2DBioFET (reprinted with permission from Ref. 157 ), (c) schematic of the electrochemical sensing platform for COVID-19 (reprinted with permission from Ref. 160 ).

One of the distinguishing characteristics of GO is its ability to transform stem cells into bone-generating cells known as osteoblasts. Porous 3D graphene-based scaffolds can be used for bone repair via bone tissue engineering. 161 A porous GO scaffolding was seeded with stem cells from mouse bone marrow. After 9 days, the cell number on the 3D GO scaffolds had increased by approximately 8.5-fold, which could be a new possible research direction to regenerate bone tissue.

Face masks have become a critical tool in the fight against the COVID-19 pandemic. 162 – 165 Huang et al. discovered that, when combined with the photothermal effect of the graphene layer, the bacterial inhibition rate could be improved by up to 80% in antibacterial masks modified with laser-induced graphene, resulting in 99.998% bacterial killing efficiency within 10 min. 166 A sensor made of a filter paper coated with graphene could detect COVID-19 in under 5 min 160 (Fig.  7 c). On this sensor surface, gold nanoparticles capped with ssDNA (single-stranded nucleic acids) probes specific to the SARSCoV-2 RNA were deposited. In the presence of the SARS-CoV-2 RNA, the ssDNA hybridized with these probes. The hybridization of the viral RNA with the ssDNA sequence increases the charges at the graphene–solution interface, causing a change in the sensor's electrical response. The sensor detected a significant increase in voltage in positive samples compared to negative samples, and confirmed the presence of virus with nearly 100% accuracy. In another study, graphene coatings have been reported as a promising contender for anti-biofilm formation to prevent infection in medical implants. When the graphene layer is loaded with usnic acid (a strong antibacterial additive), the coating provides long-term anti-biofilm protection for up to 96 h. 167 The coating is highly effective against Staphylococcus aureus and S. epidermidis , two common biofilm-forming bacteria on medical implants.

Batteries and Supercapacitors

Lithium-based batteries are acknowledged as one of the promising substitutes for applications in energy storage systems, due to their high energy density. One of the major reasons for the degradation in high energy density lithium-ion battery cathode materials is the formation of a dendritic structure and a solid electrolyte layer during the continuous charge–discharge cycles. Recently, Chen et al. suppressed the formation of Li dendrites using laser induced graphene combined with a porous silicon oxide coating. 168 They reported an improvement in the average coulombic efficiency to 99.3% (2.0 mAh cm −2  at 2.0 mA cm −2 ) compared to bare electrodes.

The lithium–sulfur (Li–S) battery is yet another promising candidate for next-generation rechargeable batteries. However, during the discharge cycle, the intermediate lithium polysulfide species dissociate in the electrolyte and diffuse between the cathode and anode, typically known as the shuttling effect, resulting in poor coulombic efficiency and rapidly reducing the capacity of the Li–S cells. The incorporation of a GO membrane to the sulfur cathode acted as an effective separator and reduced the cyclic capacity decay rate from 0.49% to 0.23%. 169 Laser scribed graphene, having a hierarchically 3-D porous structure, can greatly suppress polysulfide shuttling. 170 The resultant Li–S cell showed a high specific capacity of 1160 mAh/g with excellent cycling stability of 80.4% capacity retention after 100 cycles (Fig.  8 a, b).

(a) Schematic of a Li–S battery, (b) cycling stability of Li–S cells (reprinted with permission from Ref. 170 ), (c) cycling stability and coulombic efficiency measured at 5.2 A g −1  over 10,000 cycles, (d) Ragone plot (reprinted with permission from Ref. 171 ).

Graphene is frequently proposed as a substitute for activated carbon in supercapacitors due to its high relative surface area of 2,630 m 2 /g, which is superior for storing an electrostatic charge with almost no degradation over long-term cycling. Jayaramulu et al. created a highly efficient graphene hybrid supercapacitor by combining graphene as an electrostatic electrode and a metal–organic framework as an electrochemical electrode. The device can deliver an energy density of up to 73 Wh/kg and a power density of up to 16 kW/kg, which are comparable to Pb-acid batteries and nickel metal hydride batteries. Furthermore, standard batteries (such as lithium) have a useful life of approximately 5000 cycles. However, even after 10,000 cycles, this new hybrid graphene supercapacitor retains 88% of its capacity (Fig.  8 c, d). 171

Ink-based graphene is emerging as a new technology for scalable manufacturing of printed and wearable electronics. Gaur et al. used graphene aerosol ink to print micro-supercapacitor, which showed a volumetric capacitance of 3.25 F/cm 3  at a current density of 20 mA/cm 3 with ∼80% capacitance retention after 10,000 cycles. 172 In a similar approach, Yun et al. developed graphene ink to print an extremely flexible and durable supercapacitor. 173 This micro-supercapacitor exhibited a power density of ~ 1.13 kW/kg and specific capacitance of ~ 22 F/g at a scan rate of 100 mV/s. Additionally, it is capable of being attached to power electronic devices, such as wearable skin sensors, which can be utilized for remote medical monitoring and diagnosis.

Graphene Commercialization from Laboratory to Market

The commercialization of graphene is moving quite rapidly, with several real-world products on the horizon, and this trend is expected to accelerate in the coming years. For instance, in the sports industry, graphene is used to produce helmets, clothing, and tennis racquets. 174 Combining the mechanical and thermal benefits of graphene, an Italian-made graphene-enhanced motorcycle helmet was released in October 2016 in collaboration with the Italian Institute of Technology and the luxury design firm, Momodesign. 175 Graphene is applied as a coating to the exterior of the helmet, resulting in enhanced heat dissipation and increased user comfort. Graphene can improve the energy distribution and weight of a tennis racquet, as well as the speed and stability of the serve. 176 The tennis equipment manufacturer, Head, has already developed Graphene 360, a series of graphene-enhanced commercially available racquets. The British sportswear manufacturer, Inov-8, has produced the G-Series range of graphene-enhanced shoes as well as a pair of graphene-infused hiking boots. Utilizing graphene fibers in textiles produces antibacterial, antistatic clothing that can retain heat and block UV rays. 177 Companies such as Reebok, Direct Plus, and Versarien are already working on launching a new apparel collection that uses graphene in fabrics to help retain heat. Table III shows graphene-based products available in the market.

Market availability of graphene-based products

A number of advantages of graphene, including its high surface area, chemical stability, thermal and electrical conductivities, super-hydrophobicity, flexibility, and so on have been discussed to illustrate the viability of bridging the nano-scale features of graphene to practical human-scale applications. To aid in the ongoing advancement of graphene-based materials and devices, this paper reviews the recent advances in their synthesis and applications. In terms of synthesis, various approaches have been successfully developed, indicating the feasibility of producing high-performance, high-quality, and large-area graphene. Exfoliation, chemical reduction of GO, CVD and thermal degradation of SiC, unzipping of CNTs, and other processes are among them. The CVD growth technique, among these, can generate large sheets of graphene with few or no defects and good conductivity; however, it must be taken into consideration that the quality of the material can be highly influenced by the process parameters used during the CVD growth. The exfoliation approach is compatible with industry-scale manufacturing of graphene powder, with certain methods yielding more than 50%. The qualities and performance of synthesized graphene have been demonstrated to be substantially reliant on the type of reducing agents and the synthetic process used. In terms of its practical uses, the properties of graphene have garnered much interest in a wide variety of different application domains. Graphene is commonly employed in transparent displays due to its excellent conductivity and flexibility. Because of its high sensitivity, graphene is utilized as a sensor in medical devices, particularly to detect certain viruses such as COVID-19 and malaria. Graphene is used in protective coatings for metals due to its corrosion and oxidation resistance, and, due to its high surface area and nonflammable nature, it is used as an electrode material for electrochemical energy storage devices, such as lithium batteries and supercapacitors to improve device performance when compared to those that use traditional carbon as electrode materials.

Acknowledgements

The authors acknowledge the financial support of the Science and Engineering Research Board (SERB), India (Grant No. EMR/2016/001282).

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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Graphene Nanoelectronics pp 435–464 Cite as

Graphene Oxide: Synthesis, Characterization, Electronic Structure, and Applications

• Derek A. Stewart 2 &
• K. Andre Mkhoyan 3  
• First Online: 01 January 2012

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2 Citations

Part of the book series: NanoScience and Technology ((NANO))

While graphite oxide was first identified in 1855 [1, 2], the recent discovery of stable graphene sheets has led to renewed interest in the chemical structure and potential applications of graphene oxide sheets. These structures have several physical properties that could aid in the large scale development of a graphene electronics industry. Depending on the degree of oxidization, graphene oxide layers can be either semiconducting or insulating and provide an important complement to metallic graphene layers. In addition, the electronic and optical properties of these films can be controlled by the selective removal or addition of oxygen. For example, selective oxidationof graphene sheets could lead to electronic circuit fabrication on the scale of a single atomic layer. Graphene oxide is also dispersible in water and other solvents and this provides a facile route for graphene deposition on a wide range of substrates for macroelectronics applications. Although graphite oxide has been known for roughly 150 years, key questions remain in regards to its chemical structure, electronic properties, and fabrication. Answering these issues has taken on special urgency with the development of graphene electronics. In this chapter, we will provide an overview of the field with special focus on synthesis, characterization, and first principles analysis of bonding and electronic structures. Finally, we will also address some of the most promising applications for graphene oxide in electronics and other industries.

• Graphene Oxide
• Graphene Sheet
• Reduce Graphene Oxide
• Graphite Oxide
• Epoxy Group

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B.C. Brodie, Ann. Chim. Phys. 45 , 351 (1855)

Google Scholar  

B.C. Brodie, Phil. Trans. R. Soc. Lond. 149 , 249 (1859)

Article   Google Scholar  

K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. Grigorieva, A.A. Firsov, Science 306 , 666 (2004)

Article   ADS   Google Scholar  

A.K. Geim, K.S. Novoselov, Nat. Mater. 6 , 183 (2007)

M.Y. Han, B. Ozyilmaz, Y. Zhang, P. Kim, Phys. Rev. Lett. 98 , 206805 (2007)

Y. Zhang, T.T. Tang, C. Girit, Z. Hao, M.C. Martin, A. Zettl, M.F. Crommie, Y.R. Shen, F. Wang, Nature 459 , 820 (2009)

L. Ci, L. Song, C. Jin, D. Jariwala, D. Wu, Y. Li, A. Srivastava, Z.F. Wang, K. Storr, L. Balicas, F. Liu, P.M. Ajayan, Nat. Mater. 9 , 430 (2010)

C. Berger, Z. Song, X. Li, X. Wu, N. Brown, C. Naud, D. Mayou, T. Li, J. Hass, A.N. Marchenkov, E.H. Conrad, P.N. First, W.A. de Heer, Science 312 , 1191 (2006)

X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner, A. Velamakanni, I. Jung, E. Tutuc, S.K. Banerjee, L. Colombo, R.S. Ruoff, Science 324 , 1312 (2009)

K.S. Kim, Y. Zhao, H. Jang, S.Y. Lee, J.M. Kim, K.S. Kim, J.H. Ahn, P. Kim, J.Y. Choi, B.H. Hong, Nature 457 , 706 (2009)

A. Lerf, H. He, M. Forster, J. Klinowski, J. Phys. Chem. B 102 , 4477 (1998)

D.R. Dreyer, S. Park, C.W. Bielawski, R.S. Ruoff, Chem. Soc. Rev. 39 , 228 (2010)

O.C. Compton, S.T. Nguyen, Small 6 , 711 (2010)

U. Hofmann, R. Holst, Ber. Dtsch. Chem. Ges. B 72 , 754 (1939)

G. Ruess, Monatsh. Chem 76 , 381 (1946)

T. Nakajima, A. Mabuchi, R. Hagiwara, Carbon 26 , 357 (1988)

D. Pandey, R. Reifenberger, R. Piner, Surf. Sci. 602 , 1607 (2008)

T. Szabo, O. Berkesi, P. Forgo, K. Josepovits, Y. Sanakis, D. Petridis, I. Dekany, Chem. Mater. 18 , 2740 (2006)

W. Gao, L.B. Alemany, L. Ci, P.M. Ajayan, Nature Chem. 1 , 403 (2009)

L. Staudenmaier, Ber. Dtsch. Chem. Ges. 31 , 1481 (1898)

W.S. Hummers, U.S. Patent 2,798,878, 1957

W.S. Hummers, R.E. Offeman, J. Am. Chem. Soc. 80 , 1339 (1958)

N.I. Kovtyukhova, P.J. Ollivier, B.R. Martin, T.E. Mallouk, S.A. Chizhik, E.V. Buzaneva, A.D. Gorchinsky, Chem. Mater. 11 , 771 (1999)

M. Hirata, T. Gotou, S. Horiuchi, M. Fujiwara, M. Ohba, Carbon 42 , 2929 (2004)

J.A. Johnson, C.J. Benmore, S. Stankovich, R.S. Ruoff, Carbon 47 , 2239 (2009)

C. Petit, M. Seredych, T.J. Bandosz, J. Mater. Chem. 19 , 9176 (2009)

H.P. Boehm, W. Scholz, Justus Liebigs Ann. Chem. 691 , 1 (1965)

H.K. Jeong, Y.P. Lee, R.J.W.E. Lahaye, M.H. Park, K.H. An, I.J. Kim, C.W. Yang, C.Y. Park, R.S. Ruoff, Y.H. Lee, J. Am. Chem. Soc. 130 , 1362 (2008)

D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L.B. Alemany, W. Lu, J.M. Tour, ACS Nano 4 , 4806 (2010)

Z. Luo, Y. Lu, L.A. Somers, A.T.C. Johnson, J. Am. Chem. Soc. 131 , 898 (2009)

S. Stankovich, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Carbon 44 , 3342 (2006)

H.P. Boehm, A. Clauss, G.O. Fischer, U. Hofmann, Z. Naturforschung 17b , 150 (1962)

J. Kim, L.J. Cote, F. Kim, W. Yuan, K.R. Shull, J. Huang, J. Am Chem. Soc. 132 , 8180 (2010)

X. Wu, M. Sprinkle, X. Li, F. Ming, C. Berger, W.A. de Heer, Phys. Rev. Lett. 101 , 026801 (2008)

D.V. Kosynkin, A.L. Higginbotham, A. Sinitskii, J.R. Lomeda, A. Dimiev, B.K. Price, J.M. Tour, Nature 458 , 872 (2009)

A.L. Higginbotham, D.V. Kosynkin, A. Sinitskii, Z. Sun, J.M. Tour, ACS Nano 4 , 2059 (2010)

Z. Wei, D. Wang, S. Kim, S.Y. Kim, Y. Hu, M.K. Yakes, A.R. Laracuente, Z. Dai, S.R. Marder, C. Berger, W.P. King, W.A. de Heer, P.E. Sheenan, E. Riedo, Science 328 , 1373 (2010)

H.C. Schnieep, J.L. Li, M.J. McAllister, H. Sai, M. Herrera-Alonso, D.H. Adamson, R.K. Prud’homme, R. Car, D.A. Saville, I.A. Aksay, J. Phys. Chem. B 110 , 8535 (2006)

S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S.T. Nguygen, R.S. Ruoff, Carbon 45 , 1558 (2007)

R. Ishikawa, M. Bando, Y. Morimoto, S.Y. Park, A. Sandhu, Jpn. J. Appl. Phys. 49 , 06GC02 (2010)

G. Eda, G. Fanchini, M. Chhowalla, Nat. Nanotechnol. 3 , 270 (2008)

G.K. Ramesha, S. Sampath, J. Phys. Chem. C 113 , 7985 (2009)

G. Williams, B. Seger, P.V. Kamat, ACS Nano 2 , 1487 (2008)

L.J. Cote, R. Cruz-Silva, J. Huang, J. Am. Chem. Soc. 131 , 11027 (2009)

E.C. Salas, Z. Sun, A. Luttge, J.M. Tour, ACS Nano 4 , 4852 (2010)

X. Gao, J. Jang, S. Nagase, J. Phys. Chem. C 114 , 832 (2010)

V.C. Tung, M.J. Allen, Y. Yang, R.B. Kaner, Nat. Nanotech. 4 , 29 (2009)

D. Yang, A. Velamakanni, G. Bozoklu, S. Park, M. Stoller, R.D. Piner, S. Stankovich, I. Jung, D.A. Field, C.A. Ventrice, R.S. Ruoff, Carbon 47 , 145 (2009)

D. Ogrin, J. Chattopadhyay, A.K. Sadana, W.E. Billups, A.R. Barron, J. Am. Chem. Soc. 128 , 11322 (2006)

J. Chattopadhyay, A. Mukherjee, C.E. Hamilton, J. Kang, S. Chakraborty, W. Guo, K.F. Kelly, A.R. Barron, W.E. Billups, J. Am. Chem. Soc. 130 , 5414 (2008)

A. Bagri, R. Grantab, N.V. Medhekar, V.B. Shenoy, J. Phys. Chem. C 114 , 12053 (2010)

A. Bagri, C. Mattevi, M. Acik, Y.J. Chabal, M. Chhowalla, V.B. Shenoy, Nat. Chem. 2 , 581 (2010)

A.C.T. van Duin, S. Dasgupta, F. Lorant, W.A. Goddard, J. Phys. Chem. A 105 , 9396 (2001)

R.R. Nair, P. Blake, A.N. Grigorenko, K.S. Novoselov, T.J. Booth, T. Stauber, N.M.R. Peres, A.K. Geim, Science 320 , 1308 (2008)

K.S. Novoselov, D. Jiang, F. Schedin, T.J. Booth, V.V. Khotkevich, S.V. Morozov, A.K. Geim, Proc. Natl. Acad. Sci. U.S.A. 102 , 10451 (2005)

I. Jung, M. Pelton, R. Piner, D.A. Dikin, S. Stankovich, S. Watcharotone, M. Hausner, R.S. Ruoff, Nano Lett. 7 , 3569 (2007)

S. Roddaro, P. Pingue, V. Piazza, V. Pellegrini, F. Beltram, Nano Lett. 7 , 2707 (2007)

J. Kim, F. Kim, J. Huang, Mater. Today 13 , 28 (2010)

S. Stankovich, D.A. Dikin, G.H.B. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A. Stach, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Nature 442 , 282 (2006)

N.R. Wilson, P.A. Pandey, R. Beanland, R.J. Young, I.A. Kinloch, L. Gong, Z. Liu, K. Suenaga, J.P. Rourke, S.J. York, J. Sloan, ACS Nano 3 , 2547 (2009)

L. Reimer, H. Kohl, Transmission Electron Microscope: Physics of Image Formation , 5th edn. (Springer, Berlin, Heidelberg, New York, 2008)

C. Gomez-Navarro, J.C. Meyer, R.S. Sundaram, A. Chuvilin, S. Kurasch, M. Burghard, K. Kern, U. Kaiser, Nano Lett. 10 , 1144 (2010)

A.V. Crewe, J. Wall, J. Langmore, Science 168 , 1338 (1970)

P.E. Batson, N. Dellby, O.L. Krivanek, Nature 418 , 617 (2002)

P.D. Nellist, M.F. Chisholm, N. Dellby, O.L. Krivanek, M.F. Murfitt, Z.S. Szilagyi, A.R. Lupini, A. Borisevich, J.W.H. Sides, S.J. Pennycook, Science 305 , 1741 (2004)

K.A. Mkhoyan, P.E. Batson, J. Cha, W.J. Schaff, J. Silcox, Science 312 , 1354 (2006)

P.M. Voyles, D.A. Muller, J.L. Grazul, P.H. Citrin, H.J.L. Gossmann, Nature 416 , 826 (2002)

E. Abe, S.J. Pennycook, A.P. Tsai, Nature 421 , 347 (2003)

M.H. Gass, U. Bangert, A.L. Bleloch, P. Wang, R.R. Nair, A.K. Geim, Nat. Nanotechnol. 3 , 676 (2008)

T. Eberlein, U. Bangert, R.R. Nair, R. Jones, M. Gass, A.L. Bleloch, K.S. Novoselov, A. Geim, P.R. Briddon, Phys. Rev. B 77 , 233406 (2008)

K.A. Mkhoyan, A.W. Contryman, J. Silcox, D.A. Stewart, G. Eda, C. Mattevi, S. Miller, M. Chhowalla, Nano Lett. 9 , 1058 (2009)

E.J. Kirkland, Advanced Computing in Electron Microscopy (Plenum Press, NY, USA, 1998)

R.F. Egerton, Electron Energy Loss Spectroscopy in the Electron Microscope , 2nd edn. (Plenum Press, NY, USA, 1996)

D.A. Muller, D.J. Singh, J. Silcox, Phys. Rev. B 57 , 8181 (1998)

K.A. Mkhoyan, J. Silcox, E.S. Alldredge, N.W. Ashcroft, H. Lu, W.J. Schaff, L.F. Eastman, Appl. Phys. Lett. 82 , 1407 (2003)

G. Binnig, C.F. Quate, C. Gerber, Phys. Rev. Lett. 56 , 930 (1986)

F.J. Giessibl, Science 267 , 68 (1995)

S. Morita, R. Wiesendanger, E. Meyer, Noncontact Atomic Force Microscopy , 1st edn. (Springer, Berlin, Heidelberg, New York, 2002)

Book   Google Scholar  

F.J. Giessibl, Rev. Mod. Phys. 75 , 949 (2003)

I. Jung, M. Vaupel, M. Pelton, R. Piner, D.A. Dikin, S. Stankovich, J. An, R.S. Ruoff, J. Phys. Chem. C 112 , 8499 (2008)

A. Buchsteiner, A. Lerf, J. Pieper, J. Phys. Chem. B 110 , 22328 (2006)

G. Eda, M. Chhowalla, Nano Lett. 9 , 814 (2009)

S. Pang, H.N. Tsao, X. Feng, K. Mullen, Adv. Mater. 21 , 3488 (2009)

D. Briggs, M.P. Seah, Practical Surface Analysis, Auger and X-ray Photoelectron Spectroscopy , 2nd edn. (Wiley, NY, USA, 1996)

B.V. Crist, Handbook of Monochromatic XPS Spectra , 1st edn. (Wiley, NY, USA, 2000)

C. Mattevi, G. Eda, S. Agnoli, S. Miller, K.A. Mkhoyan, O. Celik, D. Mastrogiovanni, G. Granozzi, E. Garfunkel, M. Chhowalla, Adv. Funct. Mater. 19 , 2577 (2009)

C. Hontoria-Lucas, A.J.L. Peinando, J.D.D. Lopez-Gonzalez, M.L. Rojas-Cervantes, R.M. Martin-Aranda, Carbon 33 , 1585 (1995)

D.Q. Yang, E. Sacher, Langmuir 22 , 860 (2006)

D. Yang, A. Velamakanni, G. Bozoklu, S. Park, M. Stoller, R.D. Piner, S. Stankovich, I. Jung, D.A. Field, C.A. Ventrice Jr., R.S. Ruoff, Carbon 47 , 145 (2008)

A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Phys. Rev. Lett. 97 , 187401 (2006)

A. Gupta, G. Chen, P. Joshi, S. Tadigada, P.C. Eklund, Nano Lett. 6 , 2667 (2006)

Z. Ni, Y. Wang, T. Yu, Z. Shen, Nano Res. 1 , 273 (2008)

F. Tuinstra, J.L. Koenig, J. Chem. Phys. 53 , 1126 (1970)

C.Y. Su, Y. Xu, W. Zhang, J. Zhao, X. Tang, C.H. Tsai, L.J. Li, Chem. Mater. 21 , 5674 (2009)

S. Baroni, S. de Gironcoli, A.D. Corso, P. Giannozzi, Rev. Mod. Phys. 73 , 515 (2001)

K.N. Kudin, B. Ozbas, H.C. Schniepp, R.K. Prud’homme, I.A. Aksay, R. Car, Nano Lett. 8 , 36 (2008)

J.L. Li, K.N. Kudin, M.J. McAllister, R.K. Prud’homme, I.A. Aksay, R. Car, Phys. Rev. Lett. 96 , 176101 (2006)

Z.S. Wu, W. Ren, L. Gao, B. Liu, J. Zhao, H.M. Cheng, Nano Res. 3 , 16 (2010)

Z. Li, W. Zhang, Y. Luo, J. Yang, J.G. Hou, J. Am. Chem. Soc. 131 , 6320 (2009)

J.A. Yan, L. Xian, M.Y. Chou, Phys. Rev. Lett. 103 , 086802 (2009)

Z. Xu, K. Xue, Nanotechnology 21 , 045704 (2010)

D.W. Boukhvalov, M.I. Katsnelson, J. Am. Chem. Soc. 130 , 10697 (2008)

J.T. Paci, T. Belytschko, G.C. Schatz, J. Phys. Chem. 111 , 18099 (2007)

H.K. Jeong, M.H. Jin, K.P. So, S.C. Lim, Y.H. Lee, J. Phys. D: Appl. Phys. 42 , 065418 (2009)

Z. Luo, P.M. Vora, E.J. Mele, A.T.C. Johnson, J.M. Kikkawa, Appl. Phys. Lett. 94 , 111909 (2009)

G. Eda, Y.Y. Lin, C. Mattevi, H. Yamaguchi, H.A. Chen, I.S. Chen, C.W. Chen, M. Chhowalla, Adv. Mater. 22 , 505 (2010)

J. Ito, J. Nakamura, A. Natori, J. Appl. Phys. 103 , 113712 (2008)

A.B. Kaiser, C. Gomez-Navarro, R.S. Sundaram, M. Burghard, K. Kern, Nano Lett. 9 , 1787 (2009)

G. Eda, C. Mattevi, H. Yamaguchi, H.K. Kim, M. Chhowalla, J. Phys. Chem. C 113 , 15768 (2009)

G. Eda, M. Chhowalla, Adv. Mater. 22 , 2392 (2010)

C. Gomez-Navarro, R.T. Weitz, A.M. Bittner, M. Scolari, A. Mews, M. Burghard, K. Kern, Nano Lett. 7 , 3499 (2007)

T. Kobayashi, N. Kimura, J. Chi, S. Hirata, D. Hobara, Small 6 , 1210 (2010)

D. Joung, A. Chunder, L. Zhai, S.I. Khondaker, Nanotechnology 21 , 165202 (2010)

H.J. Shin, K.K. Kim, A. Benayad, S.M. Yoon, H.K. Park, I.S. Jung, M.H. Jin, H.K. Jeong, J.M. Kim, J.Y. Choi, Y.H. Lee, Adv. Funct. Mater. 19 , 1987 (2009)

S. Wang, P.J. Chia, L.L. Chua, L.H. Zhao, R.Q. Png, S. Sivaramakrishnan, M. Zhou, R.G.S. Goh, R.H. Friend, A.T.S. Wee, P.K.H. Ho, Adv. Mater. 20 , 3440 (2008)

S. Watcharotone, D.A. Dikin, S. Stankovich, R. Piner, I. Jung, G.H.B. Dommett, G. Evmenenko, S.E. Wu, S.F. Chen, C.P. Liu, S.T. Nguygen, R.S. Ruoff, Nano Lett. 7 , 1888 (2007)

S.S. Li, K.H. Tu, C.C. Lin, C.W. Chen, M. Chhowalla, ACS Nano 4 , 3169 (2010)

V. Shrotriya, G. Li, Y. Yao, C.W. Chu, Y. Yang, Appl. Phys. Lett. 88 , 073508 (2006)

M.D. Irwin, D.B. Buchholz, A.W. Bains, R.P.H. Chang, T.J. Marks, Proc. Natl. Acad. Sci. USA 105 , 2783 (2008)

S. Wang, J. Pu, D.S.H. Chan, B.J. Cho, K.P. Loh, Appl. Phys. Lett. 96 , 143109 (2010)

X.B. Lu, J.Y. Dai, Appl. Phys. Lett. 88 , 113104 (2006)

P. Simon, Y. Gogotsi, Nat. Mater. 7 , 845 (2008)

Y. Zhu, M.D. Stoller, W. Cai, A. Velamakanni, R.D. Piner, D. Chen, R.S. Ruoff, ACS Nano 4 , 1227 (2010)

Y. Zhu, S. Murali, M.D. Stoller, A. Velamakanni, R.D. Piner, R.S. Ruoff, Carbon 48 , 2118 (2010)

Y. Zhu, S. Murali, W. Cai, X. Li, J.W. Suk, J.R. Potts, R.S. Ruoff, Adv. Mater. (2010)

Y. Liu, D. Yu, C. Zeng, Z. Miao, L. Dai, Langmuir 26 , 6158 (2010)

J.T. Robinson, F.K. Perkins, E.S. Snow, Z. Wei, P.E. Sheenan, Nano Lett. 8 , 3137 (2008)

O.V. Yazyev, Rep. Prog. Phys. 73 , 056501 (2010)

T.L. Makarova, B. Sundqvist, R. Hohne, P. Esquinazi, Y. Kopelevich, P. Schaff, V. Dadydov, L.S. Kashevarova, A.V. Rakhmanina, Nature 413 , 716 (2001)

T.L. Makarova, B. Sundqvist, R. Hohne, P. Esquinazi, Y. Kopelevich, P. Schaff, V. Dadydov, L.S. Kashevarova, A.V. Rakhmanina, Nature 440 , 707 (2006)

P. Esquinazi, D. Spemann, R. Hohne, A. Setzer, K.H. Han, T. Butz, Phys. Rev. Lett. 91 , 227201 (2003)

Y. Kopelevich, P. Esquinazi, J.H.S. Torres, S. Moehlecke, J. Low Temp. Phys. 119 , 691 (2000)

M. Wang, C.M. Li, New J. of Phys. 12 , 083040 (2010)

Y.W. Son, M.L. Cohen, S.G. Louie, Phys. Rev. Lett. 97 , 216803 (2006a)

Y.W. Son, M.L. Cohen, S. Louie, Nature 444 , 347 (2006b)

S.S. Rao, A. Stesmans, D.V. Kosynkin, A. Higginbotham, J.M. Tour, Arxiv 1006.4942 , v1 (2010)

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Acknowledgements

D.A.S. gratefully acknowledges support through the National Science Foundation for the National Nanostructure Infrastructure Network (NNIN) and the Cornell Nanoscale Science and Technology Facility. A portion of the density functional calculations discussed in this chapter were calculated using the Intel Cluster at the Cornell Nanoscale Facility. K. A. M. acknowledges partial financial support from the Abu Dhabi-Minnesota Institute for Research Excellence (AD-MIRE); a partnership between the Petroleum Institute of Abu Dhabi and the Department of Chemical Engineering and Materials Science of the University of Minnesota. The authors also thank collaborators Prof. M. Chhowalla, Dr. C. Mattevi at Rutgers University and Prof. J. Silcox, Prof. S. Tiwari at Cornell University for many fruitful discussions.

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Stewart, D.A., Mkhoyan, K.A. (2011). Graphene Oxide: Synthesis, Characterization, Electronic Structure, and Applications. In: Raza, H. (eds) Graphene Nanoelectronics. NanoScience and Technology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-22984-8_14

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