▎ 摘　　要

Strong in-plane bonding (covalent) and weak van der Waals (vdW) interplanar interactions characterize a number of layered solids, as epitomized by graphite. The advent of graphene (Gr), individual atomic two-dimensional (2D) layers, isolated from mineral graphite via micromechanical exfoliation enabled the ability to pick, place and stack of arbitrary compositions. Moreover, this discovery implicated an access to other 2D vdW solids beyond graphene and artificially stacking atomic layers forming heterostructures/superlattices. Raman spectroscopy (RS) is a fast reliable non-destructive analytical tool and an integral part for lattice dynamical structural characterization of crystalline solids at nanoscale, revealing not only the collective atomic/molecular motions but also localized vibrations/modes and specifically used to determine the number of graphene layers and of other 2D vdW solids. We present Raman spectroscopy in first-, second- and higher-order vibrational modes involving 3 and 4 phonons (overtones and combination) and mapping of graphene (mono-, bi-, tri- and few-) layers, semiconducting transition metal dichalcogenides (TMDs) [molybdenum disulfide (MoS2) and tungsten disulfide (WS2)] and wide bandgap hexagonal boron nitride (h-BN) dispersed monolayers, revealing various molecular vibrations and structural quality/disorder. First- and higher-order phonon modes are observed and analyzed in terms of Raman intensity (spatial inhomogeneity or thickness variation), band position (intrinsic mechanical strain) and intensity ratio (structural disorder) as a function of graphene layer (n). An empirical relation for G band position with n is corroborated. All of the higher order modes are observed to upshift almost linearly with n, betraying the underlying interlayer vdW interactions. These findings exemplify the evolution of structural parameters in layered materials in changing from 3- to 2- or low-dimensional regime. The results are presented in view of applications of graphene by itself and in combination that help better understanding of physical and electronic properties for nano-/optoelectronics. Copyright (c) 2015 John Wiley & Sons, Ltd.