Department of Chemistry, School of Science, Beijing Technology and Business University, Beijing 100048, China
Key Laboratory of Green Process and Engineering, Institute of Process Engineering (IPE), Chinese Academy of Sciences (CAS), Beijing 100190, China
a r t i c l e i n f o
Article history:
Received 28 September 2014
Received in revised form
15 November 2014
Accepted 19 November 2014
Available online xxx
Key words:
Graphene
Vacancy
Defect healing
Band gap modulation
Properties of defective graphene
Graphene has attracted immense investigation since its discovery. Lattice imperfections are introduced
into graphene unavoidably during graphene growth or processing. These structural defects are known to
signicantly affect electronic and chemical properties of graphene. A comprehensive understanding of
graphene defect is thus of critical importance. Here we review the major progresses made in defectrelated engineering of graphene. Firstly, we give a brief introduction on the types of defects in graphene. Secondly, the generation and healing of the graphene defects are summarized. Then, the effects of
defects on the chemical, electronic, magnetic, and mechanical properties of graphene are discussed.
Finally, we address the associated challenges and prospects on the future study of defects in graphene
and other nanocarbon materials.
Copyright 2015, The editorial ofce of Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.
1. Introduction
Graphene has raised extensive interest in the worldwide for its
extraordinary thermal, mechanical, electrical and other properties[1,2]. Among all properties, the unique electronic properties are
assumed to be the most intriguing aspect of graphene, for example,
outstanding ballistic transport properties and longest mean free
path at room temperature[3], distinctive integral and half-integral
quantum hall effect[4,5], the highest mobility to increase the
speed of devices[6], and so on. The mobility of graphene is signicantly higher than that of the widely-used Si, of approximately
1400 cm2 V1 s1. Consequently, graphene has been considered as a
candidate material for applications in post-silicon electronics.
Graphene has a honeycomb lattice structure and a unit cell that
contains two carbon atoms. Just like in carbon nanotubes, there are
two different kinds of graphene ribbon edges: armchair and zigzag,
which can inuence the electronic properties of graphene. However, most electronic applications are handicapped by the absence
of a semiconducting gap in pristine graphene. For example, devices
made from the zero-bandgap graphene are difcult to switch off,
losing the advantage of the low static power consumption of the
http://dx.doi.org/10.1016/j.jmst.2014.11.019
1005-0302/Copyright 2015, The editorial ofce of Journal of Materials Science & Technology. Published by Elsevier Limited. All rights reserved.
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Fig. 1. StoneeWales defect SW(55-77), formed by rotating a carbonecarbon bond by 90 : (a) experimental TEM image of the defect; (b) its atomic structure as obtained from our
Density functional theory (DFT) calculations (Copyright 2008 American Chemical Society)[10].
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Fig. 2. Single vacancy V1(5-9): (a) as seen in an experimental TEM image; (b) its atomic structure obtained from our DFT calculations (Copyright 2008 American Chemical
Society)[10].
Fig. 3. (a) Grain boundary defect structure consisting of pentagon-pairs and octagons in graphene grown on a Ni substrate; (b) the DFT relaxed geometry of the defect structure; (c)
the calculated adsorption energies for two domains are similar, but both are lower in energy than a third possible adsorption conguration with all carbon atoms on hollow sites
(Copyright 2010 Nature Publishing Group)[17].
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Fig. 4. Different edge reconstructions in graphene: (a) reconstructed zigzag; (b) armchair edge; (c) (677) reconstructed armchair edge; (d) zigzag edge (Copyright 2008 American
Physical Society)[23].
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Fig. 5. Schematic illustration of the experimental setups for creating defects on graphene. The samples were formed by subsequent transfer of 12C and 13C graphene sheets on Si/
SiO2 substrate and irradiated by Ar ions with various doses followed by Raman probing. The right panel is a snapshot from molecular dynamics simulations showing a typical
atomic conguration after an ion impact (Copyright 2013 WILEY-VCH Verlag GmbH & Co. KGaA)[35].
important for generating carbon nanostructures with high electrical and thermal conductivities and, potentially, enhanced
mechanical strength.
4.1. Thermal annealing
One promising approach for removing crystalline lattice defects
and restoring graphitic structures is high temperature processing in
the presence of a hydrocarbon gas. Utilizing appropriate conditions,
the hydrocarbon gas might decompose to supply carbon atoms that
pez et al. demonstrated that
can repair defective sites. Recently, Lo
chemical vapor deposition (CVD) processing of chemically derived
graphene lms using ethylene carbon source improved lm conductivity by two orders of magnitude, to room temperature (RT)
values of 10e350 S cm1. The authors attributed the improvement
to defect healing[47]. In addition, direct observation of the modication of defective sites on graphitic surfaces under gaseous hydrocarbon atmospheres was reported by Liu et al. [48]. They studied
the reactivity of defects on highly oriented pyrolytic graphite
(HOPG) surfaces exposed to acetylene at elevated temperatures by
scanning tunneling microscopy (STM).
4.2. Self-healing
By using rst-principles calculations based on densityfunctional theory, Tsetseris et al. found that pairs of C adatoms
Fig. 6. A diagram of the vacancy migration between graphene layers leads to vacancies holes formation in one layer and the self-healing of other layers (Copyright 2014 the Royal
Society of Chemistry)[50].
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Fig. 7. Schematic view of the vacancy healing and N-doping process of graphene with
vacancies by CO and NO molecules (Copyright 2011 American Physical Society)[51].
Fig. 8. Graphene sheet in the presence of the Ni lattice: (a) side and top views of the initial congurations; equilibrium congurations at (b) 1000 and (c) 2500 K (Copyright 2010
American Chemical Society)[52].
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Fig. 9. Schematic of strained graphene functionalization: (a) after being transferred to polydimethylsiloxane (PDMS), the polycrystalline graphene is strained by elongation; (b)
after strain is applied, the aqueous solution of aryl diazonium salt is pipetted onto the graphene surface, the inset shows a photograph of several droplets on a graphene/PDMS
substrate; (c) after functionalization, the solution is removed and the substrate rinsed and dried. Because of the increased reactivity of defect sites along boundaries, there is an
increased concentration of functional molecules at these locations. (Copyright 2013 American Chemical Society)[67].
6. Concluding Remarks
Acknowledgments
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References
[1] A.K. Geim, Science 324 (2009) 1530e1534.
[2] D. Jariwala, V.K. Sangwan, L.J. Lauhon, T.J. Marks, M.C. Hersam, Chem. Soc. Rev.
42 (2013) 2824e2860.
[3] D. Gunlycke, H.M. Lawler, C.T. White, Phys. Rev. B 75 (2007) 085418.
[4] K.S. Novoselov, Z. Jiang, Y. Zhang, S.V. Morozov, H.L. Stormer, U. Zeitler,
J.C. Maan, G.S. Boebinger, P. Kim, A.K. Geim, Science 315 (2007) 1379.
[5] Y. Zhang, Y.W. Tan, H.L. Stormer, P. Kim, Nature 438 (2005) 201e204.
[6] X. Du, I. Skachko, A. Barker, E.Y. Andrei, Nat. Nanotechnol. 3 (2008) 491e495.
[7] F. Schwierz, Nat. Nanotechnol. 5 (2010) 487e496.
[8] F. Banhart, J. Kotakoski, A.V. Krasheninnikov, ACS Nano 5 (2011) 26e41.
[9] M.H. Gass, U. Bangert, A.L. Bleloch, P. Wang, R.R. Nair, A.K. Geim, Nat. Nanotechnol. 3 (2008) 676e681.
[10] J.C. Meyer, C. Kisielowski, R. Erni, M.D. Rossell, M.F. Crommie, A. Zettl, Nano
Lett. 8 (2008) 3582e3586.
[11] A.V. Krasheninnikov, P.O. Lehtinen, A.S. Foster, R.M. Nieminen, Chem. Phys.
Lett. 418 (2006) 132e136.
[12] Z. Liang, Z. Xu, T. Yan, F. Ding, Nanoscale 6 (2014) 2082e2086.
[13] J. Kotakoski, A.V. Krasheninnikov, K. Nordlund, Phys. Rev. B 74 (2006) 245420.
[14] K. Kim, H. Lee, R.W. Johnson, J.T. Tanskanen, N. Liu, M. Kim, C. Pang, C. Ahn,
S.F. Bent, Z. Bao, Nat. Commun. 5 (2014) 4781, http://dx.doi.org/10.1038/
ncomms5781.
[15] J. Coraux, A.T.N. Diaye, C. Busse, T. Michely, Nano Lett. 8 (2008) 565e570.
[16] J. Cervenka, M.I. Katsnelson, C.F.J. Flipse, Nat. Phys. 5 (2009) 840e844.
[17] J. Lahiri, Y. Lin, P. Bozkurt, I.I. Oleynik, M. Batzill, Nat. Nanotechnol. 5 (2010)
326e329.
[18] N. Ansari, F. Nazaria, F. Illas, Phys. Chem. Chem. Phys. 16 (2014) 21473e21485.
[19] O.V. Yazyev, S.G. Louie, Phys. Rev. B 81 (2010) 195420.
[20] S. Malola, H. Hakkinen, P. Koskinen, Phys. Rev. B 81 (2010) 165447.
[21] C.O. Girit, J.C. Meyer, R. Erni, M.D. Rossell, C. Kisielowski, L. Yang, C.H. Park,
M.F. Crommie, M.L. Cohen, S.G. Louie, A. Zettl, Science 323 (2009) 1705e1708.
[22] A. Chuvilin, J.C. Meyer, G. Algara-Siller, U. Kaiser, New J. Phys. 11 (2009)
083019.
[23] P. Koskinen, S. Malola, H. Hakkinen, Phys. Rev. Lett. 101 (2008) 115502.
[24] Y. Ogawa, K. Komatsu, K. Kawahara, M. Tsuji, K. Tsukagoshi, H. Ago, Nanoscale
6 (2014) 7288e7294.
[25] J.H. Kim, J.H. Hwang, J. Suh, S. Tongay, S. Kwon, C.C. Hwang, J. Wu, J.Y. Park,
Appl. Phys. Lett. 103 (2013) 171604.
[26] A. Krasheninnikov, F. Banhart, Nat. Mater. 6 (2007) 723e733.
[27] M.Z. Hossain, S. Rumyantsev, M.S. Shur, A.A. Balandin, Appl. Phys. Lett. 102
(2013) 153512.
[28] J.C. Meyer, A. Chuvilin, G. Algara-Siller, J. Biskupek, U. Kaiser, Nano Lett. 9
(2009) 2683e2689.
[29] A.W. Robertson, G.D. Lee, K. He, E. Yoon, A.I. Kirkland, J.H. Warner, Nano Lett.
14 (2014) 1634e1642.
[30] 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 (2009) 706e710.
[31] O. Lehtinen, I.L. Tsai, R. Jalil, R.R. Nair, J. Keinonen, U. Kaiser, I.V. Grigorieva,
Nanoscale 6 (2014) 6569e6576.
[32] M.M. Lucchese, F. Stavale, E.H. Martins Ferreira, C. Vilani, M.V.O. Moutinho,
R.B. Capaz, C.A. Achete, A. Jorio, Carbon 48 (2010) 1592e1597.
[33] E. Stolyarova, D. Stolyarov, K. Bolotin, S. Ryu, L. Liu, K.T. Rim, M. Klima,
M. Hybertsen, I. Pogorelsky, I. Pavlishin, K. Kusche, J. Hone, P. Kim,
H.L. Stormer, V. Yakimenko, G. Flynn, Nano Lett. 9 (2009) 332e337.
[34] J.H. Chen, W.G. Cullen, C. Jang, M.S. Fuhrer, E.D. Williams, Phys. Rev. Lett. 102
(2009) 236805.
[35] M. Kalbac, O. Lehtinen, A.V. Krasheninnikov, J. Keinonen, Adv. Mater. 25
(2013) 1004e1009.
[36] O. Lehtinen, J. Kotakoski, A.V. Krasheninnikov, A. Tolvanen, K. Nordlund,
J. Keinonen, Phys. Rev. B 81 (2010) 153401.
[37] M.C. Lemme, D.C. Bell, J.R. Williams, L.A. Stern, B.W.H. Baugher, P. JarilloHerrero, C.M. Marcus, ACS Nano 3 (2009) 2674e2676.
[38] S. Chen, D. Chen, G. Wu, Macromol. Rapid Commun. 27 (2006) 882e887.
[39] A. Bagri, C. Mattevi, M. Acik, Y.J. Chabal, M. Chhowalla, V.B. Shenoy, Nat. Chem.
2 (2010) 581e587.
[40] R. Balog, B. Jrgensen, L. Nilsson, M. Andersen, E. Rienks, M. Bianchi,
M. Fanetti, E. Lgsgaard, A. Baraldi, L. Lizzit, Nat. Mater. 9 (2010) 315e317.
pez-Sancho, M.A.H. Vozmediano, Phys. Rev. Lett. 104
[41] E.V. Castro, M.P. Lo
(2010) 036802.
[42] D.A. Dikin, S. Stankovich, E.J. Zimney, R.D. Piner, G.H.B. Dommett,
G. Evmenenko, S.T. Nguyen, R.S. Ruoff, Nature 448 (2007) 457e460.
mez-Rodriguez, Phys. Rev. Lett. 104
[43] M.M. Ugeda, I. Brihuega, F. Guinea, J.M. Go
(2010) 096804.
hne, D. Spemann, P. Esquinazi, M. Ungureanu,
[44] H. Ohldag, T. Tyliszczak, R. Ho
T. Butz, Phys. Rev. Lett. 98 (2007) 187204.
[45] K. Kim, H.J. Park, B.C. Woo, K.J. Kim, G.T. Kim, W.S. Yun, Nano Lett. 8 (2008)
3092e3096.
mez-Navarro, R.S. Sundaram, M. Burghard, K. Kern, Nano Lett.
[46] A.B. Kaiser, C. Go
9 (2009) 1787e1792.
pez, R.S. Sundaram, C. Go
mez-Navarro, D. Olea, M. Burghard, J. Go
mez[47] V. Lo
Herrero, F. Zamora, K. Kern, Adv. Mater. 21 (2009) 4683, http://dx.doi.org/
10.1002/adma.200901582.
[48] L. Liu, K.T. Rim, D. Eom, T.F. Heinz, G.W. Flynn, Nano Lett. 8 (2008) 1872e1878.
[49] L. Tsetseris, S.T. Pantelides, J. Phys. Chem. B 113 (2009) 941e944.
[50] L. Liu, J. Gao, X. Zhang, T. Yan, F. Ding, Nanoscale 6 (2014) 5729e5734.
[51] B. Wang, S.T. Pantelides, Phys. Rev. B 83 (2011) 245403.
[52] S. Karoui, H. Amara, C. Bichara, F. Ducastelle, ACS Nano 4 (2010) 6114e6120.
[53] D.W. Boukhvalov, M.I. Katsnelson, Nano Lett. 8 (2008) 4373e4379.
[54] G. Cantele, Y.S. Lee, D. Ninno, N. Marzari, Nano Lett. 9 (2009) 3425e3429.
[55] X. Peng, R. Ahuja, Nano Lett. 8 (2008) 4464e4468.
[56] P.A. Denis, F. Iribarne, J. Phys. Chem. C 117 (2013) 19048e19055.
[57] C. Park, H. Yang, A.J. Mayne, G. Dujardin, S. Seo, Y. Kuk, J. Ihm, G. Kim, Proc.
Natl. Acad. Sci. 108 (2011) 18622e18625.
[58] G.M. Rutter, J.N. Crain, N.P. Guisinger, T. Li, P.N. First, J.A. Stroscio, Science 317
(2007) 219e222.
[59] A.L. Friedman, H. Chun, Y.J. Jung, D. Heiman, E.R. Glaser, L. Menon, Phys. Rev. B
81 (2010) 115461.
[60] M.A. Ramos, J. Barzola-Quiquia, P. Esquinazi, A. Munoz-Martin, A. ClimentFont, M. Garcia-Hernandez, Phys. Rev. B 81 (2010) 214404.
[61] Y. Wang, Y. Huang, Y. Song, X. Zhang, Y. Ma, J. Liang, Y. Chen, Nano Lett. 9
(2009) 220e224.
[62] D. Zhan, J. Yan, L. Lai, Z. Ni, L. Liu, Z. Shen, Adv. Mater. 24 (2012) 4055e4069.
[63] K.K. Saxena, A. Lal, Procedia Eng. 38 (2012) 2347e2355.
[64] A.O. Monteiro, P.B. Cachim, P.M.F.J. Costa, Diam. Relat. Mater. 44 (2014)
11e25.
[65] F. Ding, K. Jiao, M. Wu, B.I. Yakobson, Phys. Rev. Lett. 98 (2007) 075503.
[66] B.P. Uberuaga, S.J. Stuart, A.F. Voter, Phys. Rev. B 75 (2007) 014301.
[67] M.A. Bissett, S. Konabe, S. Okada, M. Tsuji, H. Ago, ACS Nano 7 (2013)
10335e10343.
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