3 © 2014 Woodhead Publishing Limited 1 Epitaxial growth of graphene on silicon carbide (SiC) H. H U A N G, National University of Singapore, Singapore, S. C H E N, Nanyang Technological University, Singapore and A. T. S. WEE and W. C H E N, National University of Singapore, Singapore DOI: 10.1533/9780857099334.1.3 Abstract: This chapter provides an overview of the epitaxial growth of graphene films on various silicon carbide (SiC) substrates, their growth mechanism, and atomic scale characterization. The chapter focuses on the growth of epitaxial graphene (EG) via the thermal decomposition of single-crystal SiC in ultrahigh vacuum (UHV) and under ambient pressure. There is also a discussion of the thermal decomposition of polycrystalline SiC thin films and the intercalation methods used to produce EG. Key words: thermal decomposition, epitaxial graphene, silicon carbide. 1.1 Introduction The realization of technologically feasible graphene-based electronic, optoelectronic, chemical- and bio-sensing devices greatly relies on the development of large-scale production of high-quality graphene thin films. In the last few years, intensive research efforts have been devoted to methods for production of single-layer or few-layer graphene films, including the micromechanical exfoliation from bulk graphite using sticky tape, 1,2 chemical exfoliation from bulk graphite powders, 3 chemical or physical reduction from graphene oxides, 4–7 chemical vapour deposition of hydro- carbons on transition metal substrates 8–17 such as Cu, Ni, Ru, Ir and Pt, thermal decomposition of solid carbon sources on metals, semiconductors or insulators substrates, and thermal decomposition of commercial silicon carbide (SiC) substrates in vacuum or under atmospheric pressure conditions. 18,19 Epitaxial graphene (EG) films thermally grown on SiC can be patterned using CMOS-compatible nanolithography methods, making it compatible with current semiconductor technology and hence a promising growth process for future graphene-based devices. 20,21 In particular, high- performance devices, such as field-effect transistors, 22 photodetectors, 23 and chemical sensors 24 have been demonstrated using EG on SiC. The aim of this chapter is to provide an overview of the epitaxial growth of graphene