The atomic edge structure of graphene governs its unique electronic properties with applications in nanoscale electronics and optoelectronics. To fully realize its potential, it is critical to develop a precision etching process producing graphene edges along desired directions. Here, we present a novel approach utilizing scanning probe lithography (SPL) facilitated by a mechanochemical atomic attrition process. This technique enables the fabrication of nanopatterns in single-layer graphene from graphene edges, precisely along the crystallographic orientation of zigzag (ZZ) and armchair (AC) edges, without inducing mechanical damage to the surrounding area. Density functional theory (DFT) calculations revealed that the dissociation of C‒C bonds by the SPL probe is mediated by the formation of interfacial bridge bonds between the graphene edge and the reactive silica surface. This SPL-based mechanochemical etching method enables the construction of various nanodevice structures with specific edge orientations, which allows the exploitation of their electronic properties.
Lemme M C, Bell D C, Williams J R, Stern L A, Baugher B W H, Jarillo-Herrero P, Marcus C M. Etching of graphene devices with a helium ion beam. ACS Nano 3(9): 2674–2676 (2009)
Xu W T, Lee T W. Recent progress in fabrication techniques of graphene nanoribbons. Mater Horiz 3(3): 186–207 (2016)
Vicarelli L, Heerema S J, Dekker C, Zandbergen H W. Controlling defects in graphene for optimizing the electrical properties of graphene nanodevices. ACS Nano 9(4): 3428–3435 (2015)
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 120(21): 216601 (2018)
Lukas M, Meded V, Vijayaraghavan A, Song L, Ajayan P M, Fink K, Wenzel W, Krupke R. Catalytic subsurface etching of nanoscale channels in graphite. Nat Commun 4(1): 1379 (2013)
Sun T, Fabris S. Mechanisms for oxidative unzipping and cutting of graphene. Nano Lett 12(1): 17–21 (2012)
Liu Y Q, Jiang Y L, Sun J H, Wang Y, Qian L M, Kim S H, Chen L. Inverse relationship between thickness and wear of fluorinated graphene: “Thinner is better”. Nano Lett 22(14): 6018–6025 (2022)
Garcia R, Knoll A W, Riedo E. Advanced scanning probe lithography. Nat Nanotechnol 9(8): 577–587 (2014)
Sandoz-Rosado E J, Tertuliano O A, Terrell E J. An atomistic study of the abrasive wear and failure of graphene sheets when used as a solid lubricant and a comparison to diamond-like-carbon coatings. Carbon 50(11): 4078–4084 (2012)
Vasić B, Matković A, Gajić R, Stanković I. Wear properties of graphene edges probed by atomic force microscopy based lateral manipulation. Carbon 107: 723–732 (2016)
Jiang Y, Guo W L. Convex and concave nanodots and lines induced on HOPG surfaces by AFM voltages in ambient air. Nanotechnology 19(34): 345302 (2008)
Tapasztó L, Dobrik G, Lambin P, Biró L P. Tailoring the atomic structure of graphene nanoribbons by scanning tunnelling microscope lithography. Nat Nanotechnol 3(7): 397–401 (2008)
Chen L, Wen J L, Zhang P, Yu B J, Chen C, Ma T B, Lu X C, Kim S H, Qian L M. Nanomanufacturing of silicon surface with a single atomic layer precision via mechanochemical reactions. Nat Commun 9(1): 1542 (2018)
Li J J, Li J F, Luo J B. Superlubricity of graphite sliding against graphene nanoflake under ultrahigh contact pressure. Adv Sci 5(11): 1800810 (2018)
Li J J, Gao T Y, Luo J B. Superlubricity of graphite induced by multiple transferred graphene nanoflakes. Adv Sci 5(3): 1700616 (2018)
Cui T, Mukherjee S, Sudeep P M, Colas G, Najafi F, Tam J, Ajayan P M, Singh C V, Sun Y, Filleter T. Fatigue of graphene. Nat Mater 19(4): 405–411 (2020)
Lee C G, Wei X D, Kysar J W, Hone J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321(5887): 385–388 (2008)
Wang L F, Duan F L. Nanoscale wear mechanisms of few-layer graphene sheets induced by interfacial adhesion. Tribol Int 123: 266–272 (2018)
Xiao C, Chen C, Yao Y Y, Liu H S, Chen L, Qian L M, Kim S H. Nanoasperity adhesion of the silicon surface in humid air: The roles of surface chemistry and oxidized layer structures. Langmuir 36(20): 5483–5491 (2020)
Chen L, Qian L M. Role of interfacial water in adhesion, friction, and wear—A critical review. Friction 9(1): 1–28 (2021)
Weng L S, Zhang L Y, Chen Y P, Rokhinson L P. Atomic force microscope local oxidation nanolithography of graphene. Appl Phys Lett 93(9): 093107 (2008)
Fujihara M, Inoue R, Kurita R, Taniuchi T, Motoyui Y, Shin S, Komori F, Maniwa Y, Shinohara H, Miyata Y. Selective formation of zigzag edges in graphene cracks. ACS Nano 9(9): 9027–9033 (2015)
Yin H Q, Qi H J, Fan F F, Zhu T, Wang B L, Wei Y J. Griffith criterion for brittle fracture in graphene. Nano Lett 15(3): 1918–1924 (2015)
Yan W M, Bhuiyan F H, Tang C, Wei L, Jiang Y L, Jang S, Liu Y Q, Wu J, Wang W, Wang Y, et al. Understanding and preventing lubrication failure at the carbon atomic steps. Small 19(37): 2301515 (2023)
Ma L, Wang J L, Ding F. Strain-induced orientation-selective cutting of graphene into graphene nanoribbons on oxidation. Angew Chem-Ger Edit 124(5): 1187–1190 (2012)
Jacobs T D B, Carpick R W. Nanoscale wear as a stress-assisted chemical reaction. Nat Nanotechnol 8(2): 108–112 (2013)
Luo C S, Jiang Y L, Liu Y Q, Wang Y, Sun J H, Qian L M, Chen L. Role of interfacial bonding in tribochemical wear. Front Chem 10: 852371 (2022)
Wang Y, Xu J X, Ootani Y, Ozawa N, Adachi K, Kubo M. Non-empirical law for nanoscale atom-by-atom wear. Adv Sci 8(2): 2002827 (2021)
Qu C Y, Shi D W, Chen L, Wu Z H, Wang J, Shi S L, Gao E L, Xu Z P, Zheng Q S. Anisotropic fracture of graphene revealed by surface steps on graphite. Phys Rev Lett 129(2): 026101 (2022)
Ma L, Wang J L, Yip J, Ding F. Mechanism of transition-metal nanoparticle catalytic graphene cutting. J Phys Chem Lett 5(7): 1192–1197 (2014)
Gotsmann B, Lantz M A. Atomistic wear in a single asperity sliding contact. Phys Rev Lett 101(12): 125501 (2008)
Salinas Ruiz V R, Kuwahara T, Galipaud J, Masenelli-Varlot K, Hassine M B, Héau C, Stoll M, Mayrhofer L, Moras G, Martin J M, et al. Interplay of mechanics and chemistry governs wear of diamond-like carbon coatings interacting with ZDDP-additivated lubricants. Nat Commun 12(1): 4550 (2021)
Martini A, Kim S H. Activation volume in shear-driven chemical reactions. Tribol Lett 69(4): 150 (2021)
Derjaguin B V, Muller V M, Toporov Y P. Effect of contact deformations on the adhesion of particles. J Colloid Interf Sci 53(2): 314–326 (1975)
Li W, Yan Y G, Wang M H, Král P, Dai C L, Zhang J. Correlated rectification transport in ultranarrow charged nanocones. J Phys Chem Lett 8(2): 435–439 (2017)
Radha B, Esfandiar A, Wang F C, Rooney A P, Gopinadhan K, Keerthi A, Mishchenko A, Janardanan A, Blake P, Fumagalli L, et al. Molecular transport through capillaries made with atomic-scale precision. Nature 538(7624): 222–225 (2016)
Liu M, Yin X B, Ulin-Avila E, Geng B S, Zentgraf T, Ju L, Wang F, Zhang X. A graphene-based broadband optical modulator. Nature 474(7349): 64–67 (2011)
Jessen B S, Gammelgaard L, Thomsen M R, Mackenzie D M A, Thomsen J D, Caridad J M, Duegaard E, Watanabe K, Taniguchi T, Booth T J, et al. Lithographic band structure engineering of graphene. Nat Nanotechnol 14(4): 340–346 (2019)
Son Y W, Cohen M L, Louie S G. Half-metallic graphene nanoribbons. Nature 444(7117): 347–349 (2006)
Llinas J P, Fairbrother A, Borin Barin G, Shi W, Lee K, Wu S, Yong Choi B, Braganza R, Lear J, Kau N, et al. Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons. Nat Commun 8(1): 633 (2017)
Nakada K, Fujita M, Dresselhaus G, Dresselhaus M S. Edge state in graphene ribbons: Nanometer size effect and edge shape dependence. Phys Rev B 54(24): 17954–17961 (1996)
Passi V, Gahoi A, Senkovskiy B V, Haberer D, Fischer F R, Grüneis A, Lemme M C. Field-effect transistors based on networks of highly aligned, chemically synthesized N = 7 armchair graphene nanoribbons. ACS Appl Mater Inter 10(12): 9900–9903 (2018)
Yan Q M, Huang B, Yu J, Zheng F W, Zang J, Wu J, Gu B L, Liu F, Duan W H. Intrinsic current–voltage characteristics of graphene nanoribbon transistors and effect of edge doping. Nano Lett 7(6): 1469–1473 (2007)