Abstract
This work provides an effective low-cost synthesis and in-depth mechanistic study of high quality large-area nitrogen-doped graphene (NG) films. These films were synthesized using urea as nitrogen source and methane as carbon source, and were characterized by scanning electron microscopy (SEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The N doping level was determined to be 3.72 at.%, and N atoms were suggested to mainly incorporated in a pyrrolic N configuration. All distinct Raman peaks display a shift due to the nitrogen-doping and compressive strain. The increase in urea concentration broadens the D and 2D peak’s Full Width at Half Maximum (FWHM), due to the decrease of mean free path of phonons. The N-doped graphene exhibited an n-type doping behavior with a considerably high carrier mobility of about 74.1 cm2/(V s), confirmed by electrical transport measurements.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Novoselov K S. Electric field effect in atomically thin carbon films. Science, 2004, 306: 666–669
Geim A K. Graphene: Status and prospects. Science, 2009, 324: 1530–1534
Li X, Cai W, An J, et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science, 2009, 324: 1312–1314
Geim A K, Novoselov K S. The rise of graphene. Nat Mater, 2007, 6: 183–191
Balandin A A, Ghosh S, Bao W, et al. Superior thermal conductivity of single-layer graphene. Nano Lett, 2008, 8: 902–907
Balandin A A. Thermal properties of graphene and nanostructured carbon materials. Nat Mater, 2011, 10: 569–581
Chen S S, Wu Q Z, Mishra C, et al. Thermal conductivity of isotopically modified graphene. Nat Mater, 2012, 11: 203–207
Nika D L, Balandin A A. Two-dimensional phonon transport in graphene. J Phys Condens Matter, 2012, 24: 233203
Chen S D, Zhang Y, Wang J, et al. Connection between heat diffusion and heat conduction in one-dimensional systems. Sci China-Phys Mech Astron, 2013, 56: 1466–1471
Novoselov K S, Jiang Z, Zhang Y, et al. Room-temperature quantum hall effect in graphene. Science, 2007, 315: 1379–1379
Zhan D, Yan J, Lai L, et al. Engineering the electronic structure of graphene. Adv Mater, 2012, 24: 4055–4069
Hou Y X, Geng X M, Li Y Z, et al. Electrical and Raman properties of p-type and n-type modified graphene by inorganic quantum dot and organic molecule modification. Sci China-Phys Mech Astron, 2011, 54: 416–419
Deifallah M, McMillan P F, Corà F. Electronic and structural properties of two-dimensional carbon nitride graphenes. J Phys Chem C, 2008, 112: 5447–5453
Martins T, Miwa R, da Silva A, et al. Electronic and transport properties of boron-doped graphene nanoribbons. Phys Rev Lett, 2007, 98: 196803
Wei D C, Liu Y Q, Wang Y, et al. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett, 2009, 9: 1752–1758
Wang X R, Li X L, Zhang L, et al. N-doping of graphene through electrothermal reactions with ammonia. Science, 2009, 324: 768–771
Sun Z, Yan Z, Yao J, et al. Growth of graphene from solid carbon sources. Nature, 2010, 468: 549–552
Zhao L Y, He R, Rim K T, et al. Visualizing individual nitrogen dopants in monolayer graphene. Science, 2011, 333: 999–1003
Ito Y, Christodoulou C, Nardi M V, et al. Chemical vapor deposition of N-doped graphene and carbon films: The role of precursors and gas phase. Acs Nano, 2014, 8: 3337–3346
Kato T, Hatakeyama R. Direct growth of doping-density-controlled hexagonal graphene on SiO2 substrate by rapid-heating plasma CVD. Acs Nano, 2012, 6: 8508–8515
Terasawa T, Saiki K. Synthesis of nitrogen-doped graphene by plasma-enhanced chemical vapor deposition. Jpn J Appl Phys, 2012, 51: 924–941
Wang Z, Li P, Chen Y, et al. Synthesis of nitrogen-doped graphene using sole solid source by chemical vapour deposition. J Mater Chem C, 2014, doi: 10.1039/C4TC00924J
Panchokarla L S, Subrahmanyam K S, Saha S K, et al. Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv Mater, 2009, 21: 4726–4730
Sheng Z H, Shao L, Chen J J, et al. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. Acs Nano, 2011, 5: 4350–4358
Long D H, Li W, Ling L C, et al. Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide. Langmuir, 2010, 26: 16096–16102
Wang H B, Zhang C J, Liu Z H, et al. Nitrogen-doped graphene nanosheets with excellent lithium storage properties. J Mater Chem, 2011, 21: 5430–5434
Sun L, Wang L, Tian C G, et al. Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage. Rsc Adv, 2012, 2: 4498–4506
Wang Y, Shao Y Y, Matson D W, et al. Nitrogen-doped graphene and its application in electrochemical biosensing. Acs Nano, 2010, 4: 1790–1798
Shao Y Y, Zhang S, Engelhard M H, et al. Nitrogen-doped graphene and its electrochemical applications. J Mater Chem, 2010, 20: 7491–7496
Guo B, Liu Q, Chen E, et al. Controllable N-doping of graphene. Nano Lett, 2010, 10: 4975–4980
Deng D H, Pan X L, Yu L A, et al. Toward N-doped graphene via solvothermal synthesis. Chem Mater, 2011, 23: 1188–1193
Geng D S, Yang S L, Zhang Y, et al. Nitrogen doping effects on the structure of graphene. Appl Surf Sci, 2011, 257: 9193–9198
Li J Y, Ren Z Y, Zhou Y X, et al. Scalable synthesis of pyrrolic N-doped graphene by atmospheric pressure chemical vapor deposition and its terahertz response. Carbon, 2013, 62: 330–336
Wu T R, Shen H L, Sun L, et al. Nitrogen and boron doped monolayer graphene by chemical vapor deposition using polystyrene, urea and boric acid. New J Chem, 2012, 36: 1385–1391
Ferrari A C, Meyer J C, Scardaci V, et al. Raman spectrum of graphene and graphene layers. Phys Rev Lett, 2006, 97: 187401
Luo Z Q, Lim S H, Tian Z Q, et al. Pyridinic N doped graphene: Synthesis, electronic structure, and electrocatalytic property. J Mater Chem, 2011, 21: 8038–8044
Pimenta M A, Dresselhaus G, Dresselhaus M S, et al. Studying disorder in graphite-based systems by Raman spectroscopy. Phys Chem Chem Phys, 2007, 9: 1276–1291
Malard L M, Pimenta M A, Dresselhaus G, et al. Raman spectroscopy in graphene. Phys Rep, 2009, 473: 51–87
Venezuela P, Lazzeri M, Mauri F. Theory of double-resonant Raman spectra in graphene: Intensity and line shape of defect-induced and two-phonon bands. Phys Rev B, 2011, 84: 945–949
Zafar Z, Ni Z H, Wu X, et al. Evolution of Raman spectra in nitrogen doped graphene. Carbon, 2013, 61: 57–62
Pisana S, Lazzeri M, Casiraghi C, et al. Breakdown of the adiabatic Born-Oppenheimer approximation in graphene. Nat Mater, 2007, 6: 198–201
Das A, Pisana S, Chakraborty B, et al. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nat Nanotechnol, 2008, 3: 210–215
Ni Z H, Yu T, Lu Y H, et al. Uniaxial strain on graphene: Raman spectroscopy study and band-gap opening. ACS Nano, 2008, 2: 2301–2305
Ni Z H, Yu T, Luo Z Q, et al. Probing charged impurities in suspended graphene using Raman spectroscopy. ACS Nano, 2009, 3: 569–574
Eckmann A, Felten A, Mishchenko A, et al. Probing the nature of defects in graphene by Raman spectroscopy. Nano Lett, 2012, 12: 3925–3930
Zhang C K, Li Q Y, Tian B, et al. Isotope effect of the phonons mean free path in graphene by micro-Raman measurement. Sci China-Phys Mech Astron, 2014, 57: 1817–1821
Xue Y, Wu B, Jiang L, et al. Low temperature growth of highly nitrogen-doped single crystal graphene arrays by chemical vapor deposition. J Am Chem Soc, 2012, 134: 11060–11063
Jin Z, Yao J, Kittrell C, et al. Large-scale growth and characterizations of nitrogen-doped monolayer graphene sheets. Acs Nano, 2011, 5: 4112–4117
Author information
Authors and Affiliations
Corresponding author
Additional information
Recommended by ZHAO Hong (Associate Editor)
Rights and permissions
About this article
Cite this article
Zhang, C., Lin, W., Zhao, Z. et al. CVD synthesis of nitrogen-doped graphene using urea. Sci. China Phys. Mech. Astron. 58, 107801 (2015). https://doi.org/10.1007/s11433-015-5717-0
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11433-015-5717-0