Atomically sharp non-classical ripples in graphene

A fundamental property of a material is the measure of its deformation under applied stress. After studying the mechanical properties of bulk materials for the past several centuries, with the discovery of graphene and other two-dimensional materials, we are now poised to study the mechanical properties of single atom thick materials at the nanoscale. Despite a large number of theoretical investigations of the mechanical properties and rippling of single layer graphene, direct controlled experimental measurements of the same have been limited, due in part to the difficulty of engineering reproducible ripples such that relevant physical parameters like wavelength, amplitude, sheet length and curvature can be systematically varied. Here we report extreme (>10%) strain engineering of monolayer graphene by a novel technique of draping it over large Cu step edges. Nanoscale periodic ripples are formed as graphene is pinned and pulled by substrate contact forces. We use a scanning tunneling microscope to study these ripples to find that classical scaling laws fail to explain their shape. Unlike a classical fabric that forms sinusoidal ripples in the transverse direction when stressed in the longitudinal direction, graphene forms triangular ripples, where bending is limited to a narrow region on the order of unit cell dimensions at the apex of each ripple. This non-classical bending profile results in graphene behaving like a bizarre fabric, which regardless of how it is pulled, always buckles at the same angle. Using a phenomenological model, we argue that our observations can be accounted for by assuming that unlike a thin classical fabric, graphene undergoes significant stretching when bent. Our results provide insights into the atomic-scale bending mechanisms of 2D materials under traditionally inaccessible strain magnitudes and demonstrate a path forward for their strain engineering.Comment: 22 pages, 4 figure

Graphene and Beyond: Recent Advances in Two-Dimensional Materials Synthesis, Properties, and Devices

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moir\ue9 pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moir\ue9 engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field

Controlling Nitrogen Doping in Graphene with Atomic Precision: Synthesis and Characterization

Graphene provides a unique platform for the detailed study of its dopants at the atomic level. Previously, doped materials including Si, and 0D-1D carbon nanomaterials presented difficulties in the characterization of their dopants due to gradients in their dopant concentration and agglomeration of the material itself. Graphene’s two-dimensional nature allows for the detailed characterization of these dopants via spectroscopic and atomic resolution imaging techniques. Nitrogen doping of graphene has been well studied, providing insights into the dopant bonding structure, dopant-dopant interaction, and spatial segregation within a single crystal. Different configurations of nitrogen within the carbon lattice have different electronic and chemical properties, and by controlling these dopants it is possible to either n- or p-type dope graphene, grant half-metallicity, and alter nitrogen doped graphene’s (NG) catalytic and sensing properties. Thus, an understanding and the ability to control different types of nitrogen doping configurations allows for the fine tuning of NG’s properties. Here we review the synthesis, characterization, and properties of nitrogen dopants in NG beyond atomic dopant concentration

Chemical and Bio Sensing Using Graphene-Enhanced Raman Spectroscopy

Graphene is a two-dimensional (2D) material consisting of a single sheet of sp2 hybridized carbon atoms laced in a hexagonal lattice, with potentially wide usage as a Raman enhancement substrate, also termed graphene-enhanced Raman scattering (GERS), making it ideal for sensing applications. GERS improves upon traditional surface-enhanced Raman scattering (SERS), combining its single-molecule sensitivity and spectral fingerprinting of molecules, and graphene’s simple processing and superior uniformity. This enables fast and highly sensitive detection of a wide variety of analytes. Accordingly, GERS has been investigated for a wide variety of sensing applications, including chemical- and bio-sensing. As a derivative of GERS, the use of two-dimensional materials other than graphene for Raman enhancement has emerged, which possess remarkably interesting properties and potential wider applications in combination with GERS. In this review, we first introduce various types of 2D materials, including graphene, MoS2, doped graphene, their properties, and synthesis. Then, we describe the principles of GERS and comprehensively explain how the GERS enhancement factors are influenced by molecular and 2D material properties. In the last section, we discuss the application of GERS in chemical- and bio-sensing, and the prospects of such a novel sensing method

Atomistic-Scale Simulations on Graphene Bending Near a Copper Surface

Molecular insights into graphene-catalyst surface interactions can provide useful information for the efficient design of copper current collectors with graphitic anode interfaces. As graphene bending can affect the local electron density, it should reflect its local reactivity as well. Using ReaxFF reactive molecular simulations, we have investigated the possible bending of graphene in vacuum and near copper surfaces. We describe the energy cost for graphene bending and the binding energy with hydrogen and copper with two different ReaxFF parameter sets, demonstrating the relevance of using the more recently developed ReaxFF parameter sets for graphene properties. Moreover, the draping angle at copper step edges obtained from our atomistic simulations is in good agreement with the draping angle determined from experimental measurements, thus validating the ReaxFF results

Atomistic-Scale Simulations on Graphene Bending Near a Copper Surface

Molecular insights into graphene-catalyst surface interactions can provide useful information for the efficient design of copper current collectors with graphitic anode interfaces. As graphene bending can affect the local electron density, it should reflect its local reactivity as well. Using ReaxFF reactive molecular simulations, we have investigated the possible bending of graphene in vacuum and near copper surfaces. We describe the energy cost for graphene bending and the binding energy with hydrogen and copper with two different ReaxFF parameter sets, demonstrating the relevance of using the more recently developed ReaxFF parameter sets for graphene properties. Moreover, the draping angle at copper step edges obtained from our atomistic simulations is in good agreement with the draping angle determined from experimental measurements, thus validating the ReaxFF results