Abstract
Graphene with atomically smooth and configuration-specific edges plays the key role in the performance of graphene-based electronic devices. Remote hydrogen plasma etching of graphene has been proven to be an effective way to create smooth edges with a specific zigzag configuration. However, the etching process is still poorly understood. In this study, with the aid of a custom-made plasma-enhanced hydrogen etching (PEHE) system, a detailed graphene etching process by remote hydrogen plasma is presented. Specifically, we find that hydrogen plasma etching of graphene shows strong thickness and temperature dependence. The etching process of single-layer graphene is isotropic. This is opposite to the anisotropic etching effect observed for bilayer and thicker graphene with an obvious dependence on temperature. On the basis of these observations, a geometrical model was built to illustrate the configuration evolution of graphene edges during etching, which reveals the origin of the anisotropic etching effect. By further utilizing this model, armchair graphene edges were also prepared in a controlled manner for the first time. These investigations offer a better understanding of the etching process for graphene, which should facilitate the fabrication of graphene-based electronic devices with controlled edges and the exploration of more interesting properties of graphene.
Similar content being viewed by others
References
Colombo, L.; Wallace, R. M.; Ruoff, R. S. Graphene growth and device integration. Proc. IEEE 2013, 101, 1536–1556.
Das Sarma, S.; Adam, S.; Hwang, E. H.; Rossi, E. Electronic transport in two-dimensional graphene. Rev. Mod. Phys. 2011, 83, 407–470.
Han, M. Y.; Özyilmaz, B.; Zhang, Y. B.; Kim, P. Energy band-gap engineering of graphene nanoribbons. Phys. Rev. Lett. 2007, 98, 206805.
Kim, K.; Choi, J. Y.; Kim, T.; Cho, S. H.; Chung, H. J. A role for graphene in silicon-based semiconductor devices. Nature 2011, 479, 338–344.
Liao, L.; Duan, X. F. Graphene for radio frequency electronics. Mater. Today 2012, 15, 328–338.
Novoselov, K. S.; Fal’ko, V. I.; Colombo, L.; Gellert, P. R.; Schwab, M. G.; Kim, K. A roadmap for graphene. Nature 2012, 490, 192–200.
Bai, J. W.; Cheng, R.; Xiu, F. X.; Liao, L.; Wang, M. S.; Shailos, A.; Wang, K. L.; Huang, Y.; Duan, X. F. Very large magnetoresistance in graphene nanoribbons. Nat. Nanotechnol. 2010, 5, 655–659.
Girit, Ç. Ö.; Meyer, J. C.; Erni, R.; Rossell, M. D.; Kisielowski, C.; Yang, L.; Park, C. H.; Crommie, M. F.; Cohen, M. L.; Louie, S. G. et al. Graphene at the edge: Stability and dynamics. Science 2009, 323, 1705–1708.
Krauss, B.; Nemes-Incze, P.; Skakalova, V.; Biro, L. P.; von Klitzing, K.; Smet, J. H. Raman scattering at pure graphene zigzag edges. Nano Lett. 2010, 10, 4544–4548.
Liu, Y. Y.; Dobrinsky, A.; Yakobson, B. I. Graphene edge from armchair to zigzag: The origins of nanotube chirality? Phys. Rev. Lett. 2010, 105, 235502.
Suenaga, K.; Koshino, M. Atom-by-atom spectroscopy at graphene edge. Nature 2010, 468, 1088–1090.
Tao, C. G.; Jiao, L. Y.; Yazyev, O. V.; Chen, Y. C.; Feng, J. J; Zhang, X. W.; Capaz, R. B.; Tour, J. M.; Zettl, A.; Louie, S. G. et al. Spatially resolving edge states of chiral graphene nanoribbons. Nat. Phys. 2011, 7, 616–620.
Ziatdinov, M.; Fujii, S.; Kusakabe, K.; Kiguchi, M.; Mori, T.; Enoki, T. Visualization of electronic states on atomically smooth graphitic edges with different types of hydrogen termination. Phys. Rev. B 2013, 87, 115427.
Jiao, L. Y.; Zhang, L.; Wang, X. R.; Diankov, G.; Dai, H. J. Narrow graphene nanoribbons from carbon nanotubes. Nature 2009, 458, 877–880.
Li, X. L.; Wang, X. R.; Zhang, L.; Lee, S.; Dai, H. J. Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 2008, 319, 1229–1232.
Ruffieux, P.; Wang, S. Y.; Yang, B.; Sánchez-Sánchez, C.; Liu, J.; Dienel, T.; Talirz, L.; Shinde, P.; Pignedoli, C. A.; Passerone, D. et al. On-surface synthesis of graphene nanoribbons with zigzag edge topology. Nature 2016, 531, 489–492.
Wang, X. R.; Ouyang, Y. J.; Li, X. L.; Wang, H. L.; Guo, J.; Dai, H. J. Room-temperature all-semiconducting sub-10-nm graphene nanoribbon field-effect transistors. Phys. Rev. Lett. 2008, 100, 206803.
Yu, W. J.; Duan, X. F. Tunable transport gap in narrow bilayer graphene nanoribbons. Sci. Rep. 2013, 3, 1248.
Magda, G. Z.; Jin, X. Z.; Hagymási, I.; Vancsó, P.; Osváth, Z.; Nemes-Incze, P.; Hwang, C.; Biró, L. P.; Tapasztó, L. Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons. Nature 2014, 514, 608–611.
Cai, J.; Ruffieux, P.; Jaafar, R.; Bieri, M.; Braun, T.; Blankenburg, S.; Muoth, M.; Seitsonen, A. P.; Saleh, M.; Feng, X.; Mullen, K.; Fasel, R. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 2010, 466, 470–473.
Dobrik, G.; Tapasztó, L.; Biró, L. P. Selective etching of armchair edges in graphite. Carbon 2013, 56, 332–338.
Luo, D.; Yang, F.; Wang, X.; Sun, H.; Gao, D. L.; Li, R. M.; Yang, J.; Li, Y. Anisotropic etching of graphite flakes with water vapor to produce armchair-edged graphene. Small 2014, 10, 2809–2814.
Campos, L. C.; Manfrinato, V. R.; Sanchez-Yamagishi, J. D.; Kong, J.; Jarillo-Herrero, P. Anisotropic etching and nanoribbon formation in single-layer graphene. Nano Lett. 2009, 9, 2600–2604.
Nemes-Incze, P.; Magda, G.; Kamarás, K.; Biró, L. P. Crystallographically selective nanopatterning of graphene on SiO2. Nano Res. 2010, 3, 110–116.
Ci, L. J.; Xu, Z. P.; Wang, L. L.; Gao, W.; Ding, F.; Kelly, K. F.; Yakobson, B. I.; Ajayan, P. M. Controlled nanocutting of graphene. Nano Res. 2008, 1, 116–122.
Qi, M.; Ren, Z. Y.; Jiao, Y.; Zhou, Y. X.; Xu, X. L.; Li, W. L.; Li, J. Y.; Zheng, X. L.; Bai, J. T. Hydrogen kinetics on scalable graphene growth by atmospheric pressure chemical vapor deposition with acetylene. J. Phys. Chem. C 2013, 117, 14348–14353.
Vlassiouk, I.; Regmi, M.; Fulvio, P.; Dai, S.; Datskos, P.; Eres, G.; Smirnov, S. Role of hydrogen in chemical vapor deposition growth of large single-crystal graphene. ACS Nano 2011, 5, 6069–6076.
Zhang, X. Y.; Wang, L.; Xin, J.; Yakobson, B. I.; Ding, F. Role of hydrogen in graphene chemical vapor deposition growth on a copper surface. J. Am. Chem. Soc. 2014, 136, 3040–3047.
Zhang, Y.; Li, Z.; Kim, P.; Zhang, L.; Zhou, C. W. Anisotropic hydrogen etching of chemical vapor deposited graphene. ACS Nano 2012, 6, 126–132.
Ma, T.; Ren, W. C.; Zhang, X. Y.; Liu, Z. B.; Gao, Y.; Yin, L. C.; Ma, X. L.; Ding, F.; Cheng, H. M. Edge-controlled growth and kinetics of singlecrystal graphene domains by chemical vapor deposition. Proc. Natl. Acad. Sci. USA 2013, 110, 20386–20391.
Zhang, H. R.; Zhang, Y. H.; Zhang, Y. Q.; Chen, Z. Y.; Sui, Y. P.; Ge, X. M.; Yu, G. H.; Jin, Z.; Liu, X. Y. Edge morphology evolution of graphene domains during chemical vapor deposition cooling revealed through hydrogen etching. Nanoscale 2016, 8, 4145–4150.
Geng, D. C.; Wu, B.; Guo, Y. L.; Luo, B. R.; Xue, Y. Z.; Chen, J. Y.; Yu, G.; Liu, Y. Q. Fractal etching of graphene. J. Am. Chem. Soc. 2013, 135, 6431–6434.
Knox, K. R.; Wang, S. C.; Morgante, A.; Cvetko, D.; Locatelli, A.; Mentes, T. O.; Niño, M. A.; Kim, P.; Osgood, R. M. Jr. Spectromicroscopy of single and multilayer graphene supported by a weakly interacting substrate. Phys. Rev. B 2008, 78, 201408(R).
Yang, R.; Zhang, L. C.; Wang, Y.; Shi, Z. W.; Shi, D. X.; Gao, H. J.; Wang, E. G.; Zhang, G. Y. An anisotropic etching effect in the graphene basal plane. Adv. Mater. 2010, 22, 4014–4019.
Guo, Y. F.; Guo, W. L. Favorable zigzag configuration at etched graphene edges. J. Phys. Chem. C 2011, 115, 20546–20549.
Zhang, X. W.; Yazyev, O. V.; Feng, J. J.; Xie, L. M.; Tao, C. G.; Chen, Y. C.; Jiao, L. Y.; Pedramrazi, Z.; Zettl, A.; Louie, S. G. et al. Experimentally engineering the edge termination of graphene nanoribbons. ACS Nano 2013, 7, 198–202.
Ma, B. J.; Wang, P. Q.; Ren, S. Z.; Jia, C. C.; Guo, X. F. Versatile optical determination of two-dimensional atomic crystal layers. Carbon 2016, 109, 384–389.
Xie, L. M.; Jiao, L. Y.; Dai, H. J. Selective etching of graphene edges by hydrogen plasma. J. Am. Chem. Soc. 2010, 132, 14751–14753.
Shi, Z. W.; Yang, R.; Zhang, L. C.; Wang, Y.; Liu, D. H.; Shi, D. X.; Wang, E. G.; Zhang, G. Y. Patterning graphene with zigzag edges by self-aligned anisotropic etching. Adv. Mater. 2011, 23, 3061–3065.
Diankov, G.; Neumann, M.; Goldhaber-Gordon, D. Extreme monolayerselectivity of hydrogen-plasma reactions with graphene. ACS Nano 2013, 7, 1324–1332.
Wang, G. L.; Wu, S.; Zhang, T. T.; Chen, P.; Lu, X. B.; Wang, S. P.; Wang, D. M.; Watanabe, K.; Taniguchi, T.; Shi, D. X. et al. Patterning monolayer graphene with zigzag edges on hexagonal boron nitride by anisotropic etching. Appl. Phys. Lett. 2016, 109, 053101.
Pan, Z. J.; Yang, R. T. The mechanism of methane formation from the reaction between graphite and hydrogen. J. Catal. 1990, 123, 206–214.
Davydova, A.; Despiau-Pujo, E.; Cunge, G.; Graves, D. B. Etching mechanisms of graphene nanoribbons in downstream H2 plasmas: Insights from molecular dynamics simulations. J. Phys. D: Appl. Phys. 2015, 48, 195202.
Harpale, A.; Panesi, M.; Chew, H. B. Plasma-graphene interaction and its effects on nanoscale patterning. Phys. Rev. B 2016, 93, 035416.
Sekerka, R. F. Equilibrium and growth shapes of crystals: How do they differ and why should we care? Cryst. Res. Technol. 2005, 40, 291–306.
Artyukhov, V. I.; Liu, Y. Y.; Yakobson, B. I. Equilibrium at the edge and atomistic mechanisms of graphene growth. Proc. Natl. Acad. Sci. USA 2012, 109, 15136–15140.
Wu, S.; Liu, B.; Shen, C.; Li, S.; Huang, X. C.; Lu, X. B.; Chen, P.; Wang, G. L.; Wang, D. M.; Liao, M. Z. et al. Magnetotransport properties of graphene nanoribbons with zigzag edges. Phys. Rev. Lett. 2018, 120, 216601.
Acknowledgements
Financial support from the National Key R&D Program of China (No. 2017YFA0204901) and the National Natural Science Foundation of China (Nos. 21373014 and 21727806) is gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Ma, B., Ren, S., Wang, P. et al. Precise control of graphene etching by remote hydrogen plasma. Nano Res. 12, 137–142 (2019). https://doi.org/10.1007/s12274-018-2192-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12274-018-2192-8