Spatially Coherent Tip-Enhanced Raman Spectroscopy Measurements of Electron-Phonon Interaction in a Graphene Device.

Coherence length (Lc) of the Raman scattering process in graphene as a function of Fermi energy is obtained with spatially coherent tip-enhanced Raman spectroscopy. Lc decreases when the Fermi energy is moved into the neutrality point, consistent with the concept of the Kohn anomaly within a ballistic transport regime. Since the Raman scattering involves electrons and phonons, the observed results can be rationalized either as due to unusually large variation of the longitudinal optical phonon group velocity vg, reaching twice the value for the longitudinal acoustic phonon, or due to changes in the electron energy uncertainty, both properties being important for optical and transport phenomena that might not be observable by any other technique.

Studying 2D materials with advanced Raman spectroscopy: CARS, SRS and TERS.

Raman spectroscopy has been established as a valuable tool to study and characterize two-dimensional (2D) systems, but it exhibits two drawbacks: a relatively weak signal response and a limited spatial resolution. Recently, advanced Raman spectroscopy techniques, such as coherent anti-Stokes spectroscopy (CARS), stimulated Raman scattering (SRS) and tip-enhanced Raman spectroscopy (TERS), have been shown to overcome these two limitations. In this article, we review how useful physical information can be retrieved from different 2D materials using these three advanced Raman spectroscopy and imaging techniques, discussing results on graphene, hexagonal boron-nitride, and transition metal di- and mono-chalcogenides, thus providing perspectives for future work in this early-stage field of research, including similar studies on unexplored 2D systems and open questions.

Nanofabrication of plasmon-tunable nanoantennas for tip-enhanced Raman spectroscopy.

Plasmon-tunable tip pyramids (PTTPs) are reproducible and efficient nanoantennas for tip-enhanced Raman spectroscopy (TERS). Their fabrication method is based on template stripping of a segmented gold pyramid with a size-adjustable nanopyramid end, which is capable of supporting monopole localized surface plasmon resonance (LSPR) modes leading to high spectral enhancement when its resonance energy is matched with the excitation laser energy. Here, we describe in detail the PTTP fabrication method and report a statistical analysis based on 530 PTTPs' and 185 ordinary gold micropyramids' templates. Our results indicate that the PTTP method generates probes with an apex diameter smaller than 30 nm on 92.4% of the batch, which is a parameter directly related to the achievable TERS spatial resolution. Moreover, the PTTPs' nanopyramid edge size L, a critical parameter for LSPR spectral tuning, shows variability typically smaller than 12.5%. The PTTP's performance was tested in TERS experiments performed on graphene, and the results show a spectral enhancement of up to 72-fold, which is at least one order of magnitude higher than that typically achieved with gold micropyramids. Imaging resolution is in the order of 20 nm.

Probing Spatial Phonon Correlation Length in Post-Transition Metal Monochalcogenide GaS Using Tip-Enhanced Raman Spectroscopy.

The knowledge of the phonon coherence length is of great importance for two-dimensional-based materials since phonons can limit the lifetime of charge carriers and heat dissipation. Here we use tip-enhanced Raman spectroscopy (TERS) to measure the spatial correlation length Lc of the A1g1 and A1g2 phonons of monolayer and few-layer gallium sulfide (GaS). The differences in Lc values are responsible for different enhancements of the A1g modes, with A1g1 always enhancing more than the A1g2, independently of the number of GaS layers. For five layers, the results show an Lc of 64 and 47 nm for A1g1 and A1g2, respectively, and the coherence lengths decrease when decreasing the number of layers, indicating that scattering with the surface roughness plays an important role.

Raman evidence for pressure-induced formation of diamondene.

Despite the advanced stage of diamond thin-film technology, with applications ranging from superconductivity to biosensing, the realization of a stable and atomically thick two-dimensional diamond material, named here as diamondene, is still forthcoming. Adding to the outstanding properties of its bulk and thin-film counterparts, diamondene is predicted to be a ferromagnetic semiconductor with spin polarized bands. Here, we provide spectroscopic evidence for the formation of diamondene by performing Raman spectroscopy of double-layer graphene under high pressure. The results are explained in terms of a breakdown in the Kohn anomaly associated with the finite size of the remaining graphene sites surrounded by the diamondene matrix. Ab initio calculations and molecular dynamics simulations are employed to clarify the mechanism of diamondene formation, which requires two or more layers of graphene subjected to high pressures in the presence of specific chemical groups such as hydroxyl groups or hydrogens.The synthesis of two-dimensional diamond is the ultimate goal of diamond thin-film technology. Here, the authors perform Raman spectroscopy of bilayer graphene under pressure, and obtain spectroscopic evidence of formation of diamondene, an atomically thin form of diamond.

Passive near-field imaging with pseudo-thermal sources.

We demonstrate experimentally that spurious effects caused by interference can be eliminated in passive near-field imaging by implementing a simple random illumination. We show that typical imaging artifacts are effectively eliminated when the radiation emitted by a pseudo-thermal source illuminates the sample and the scattered field is collected by an aperture probe over essentially all angles of incidence. This novel pseudo-thermal source can be easily implemented and significantly enhances the performance of passive near-field imaging.

Characterization of Few-Layer 1T' MoTe2 by Polarization-Resolved Second Harmonic Generation and Raman Scattering.

We study the crystal symmetry of few-layer 1T' MoTe2 using the polarization dependence of the second harmonic generation (SHG) and Raman scattering. Bulk 1T' MoTe2 is known to be inversion symmetric; however, we find that the inversion symmetry is broken for finite crystals with even numbers of layers, resulting in strong SHG comparable to other transition-metal dichalcogenides. Group theory analysis of the polarization dependence of the Raman signals allows for the definitive assignment of all the Raman modes in 1T' MoTe2 and clears up a discrepancy in the literature. The Raman results were also compared with density functional theory simulations and are in excellent agreement with the layer-dependent variations of the Raman modes. The experimental measurements also determine the relationship between the crystal axes and the polarization dependence of the SHG and Raman scattering, which now allows the anisotropy of polarized SHG or Raman signal to independently determine the crystal orientation.

Giant and Tunable Anisotropy of Nanoscale Friction in Graphene.

The nanoscale friction between an atomic force microscopy tip and graphene is investigated using friction force microscopy (FFM). During the tip movement, friction forces are observed to increase and then saturate in a highly anisotropic manner. As a result, the friction forces in graphene are highly dependent on the scanning direction: under some conditions, the energy dissipated along the armchair direction can be 80% higher than along the zigzag direction. In comparison, for highly-oriented pyrolitic graphite (HOPG), the friction anisotropy between armchair and zigzag directions is only 15%. This giant friction anisotropy in graphene results from anisotropies in the amplitudes of flexural deformations of the graphene sheet driven by the tip movement, not present in HOPG. The effect can be seen as a novel manifestation of the classical phenomenon of Euler buckling at the nanoscale, which provides the non-linear ingredients that amplify friction anisotropy. Simulations based on a novel version of the 2D Tomlinson model (modified to include the effects of flexural deformations), as well as fully atomistic molecular dynamics simulations and first-principles density-functional theory (DFT) calculations, are able to reproduce and explain the experimental observations.

Observing the Angular Distribution of Raman Scattered Fields.

In conventional optical spectroscopy, lenses are used to focus light on the sample and to collect light scattered from the sample. Focusing increases the signal intensity, but it amounts to angular (k-space) averaging and leads to information loss. In this issue of ACS Nano, Budde and collaborators record radiation patterns of Raman scattering from a single layer of graphene, revealing the angular distribution of the scattered field. The authors show that the radiation patterns render the spatial symmetry of vibrational modes. Furthermore, their results demonstrate that depolarization effects occurring in the focal region must be taken into account for proper interpretation of Raman intensities. We outline here the working principle of this new approach and discuss future applications for studies of graphene and other low-dimensional systems.

Near-field Raman spectroscopy of nanocarbon materials.

Nanocarbon materials, including sp(2) hybridized two-dimensional graphene and one-dimensional carbon nanotubes, and sp(1) hybridized one-dimensional carbyne, are being considered for the next generation of integrated optoelectronic devices. The strong electron-phonon coupling present in these nanocarbon materials makes Raman spectroscopy an ideal tool to study and characterize the material and device properties. Near-field Raman spectroscopy combines non-destructive chemical, electrical, and structural specificity with nanoscale spatial resolution, making it an ideal tool for studying nanocarbon systems. Here we use near-field Raman spectroscopy to study strain, defects, and doping in different nanocarbon systems.

Strain Discontinuity, Avalanche, and Memory in Carbon Nanotube Serpentine Systems.

This work addresses the problem of how a nano-object adheres to a supporting media. The case of study are the serpentine-like structures of single-wall carbon nanotubes (SWNTs) grown on vicinal crystalline quartz. We develop in situ nanomanipulation and confocal Raman spectroscopy in such systems, and to explain the results, we propose a dynamical equation in which static friction is treated phenomenologically and implemented as cutoff for velocities, via Heaviside step function and an adhesion force tensor. We demonstrate that the strain profiles observed along the SWNTs are due to anisotropic adhesion, adhesion discontinuities, strain avalanches, and memory effects. The equation is general enough to make predictions for various one- and two-dimensional nanosystems adhered to a supporting media.

Tuning Localized Surface Plasmon Resonance in Scanning Near-Field Optical Microscopy Probes.

A reproducible route for tuning localized surface plasmon resonance in scattering type near-field optical microscopy probes is presented. The method is based on the production of a focused-ion-beam milled single groove near the apex of electrochemically etched gold tips. Electron energy-loss spectroscopy and scanning transmission electron microscopy are employed to obtain highly spatially and spectroscopically resolved maps of the milled probes, revealing localized surface plasmon resonance at visible and near-infrared wavelengths. By changing the distance L between the groove and the probe apex, the localized surface plasmon resonance energy can be fine-tuned at a desired absorption channel. Tip-enhanced Raman spectroscopy is applied as a test platform, and the results prove the reliability of the method to produce efficient scattering type near-field optical microscopy probes.

Tip-enhanced Raman mapping of local strain in graphene.

We demonstrate local strain measurements in graphene by using tip-enhanced Raman spectroscopy (TERS). We find that a single 5 nm particle can induce a radial strain over a lateral distance of ∼170 nm. By treating the particle as a point force on a circular membrane, we find that the strain in the radial direction (r) is ∝ r−(2 3),in agreement with force-displacement measurements conducted on suspended graphene flakes. Our results demonstrate that TERS can be used to map out static strain fields at the nanoscale, which are inaccessible using force-displacement techniques.

Spatial coherence in near-field Raman scattering.

Inelastic light scattering in crystals has historically been treated as a spatially incoherent process, giving rise to incoherent optical radiation. Here we demonstrate that Raman scattering can be spatially coherent, in which case it depends on the dimensionality and symmetry of the scatterer. Using near-field spectroscopy, we measure a correlation length of ∼30 nm for the optical phonons in graphene, the results varying with vibrational symmetries and spatial confinement of the phonons.

Perspectives on Raman spectroscopy of graphene-based systems: from the perfect two-dimensional surface to charcoal.

Raman spectroscopy has been already established as a powerful tool for characterizing the different types of carbon nanostructures, ranging from the highly ordered two-dimensional graphene and one-dimensional nanotubes, down to disordered materials, like nanographite and charcoal. Here we focus on the recent advances of Raman spectroscopy within carbon nanoscience. We discuss in situ nano-manipulation and Raman imaging for addressing controlled perturbations; multi-technique work for the development of nanometrology; crossing the diffraction limit with near-field optics for high resolution imaging. Finally, the applications of Raman spectroscopy in cross-referenced fields, like biotechnology and soil science, are discussed.

Raman signature of graphene superlattices.

When two identical two-dimensional periodic structures are superposed, a mismatch rotation angle between the structures generates a superlattice. This effect is commonly observed in graphite, where the rotation between graphene layers generates Moiré patterns in scanning tunneling microscopy images. Here, a study of intravalley and intervalley double-resonance Raman processes mediated by static potentials in rotationally stacked bilayer graphene is presented. The peak properties depend on the mismatch rotation angle and can be used as an optical signature for superlattices in bilayer graphene. An atomic force microscopy system is used to produce and identify specific rotationally stacked bilayer graphenes that demonstrate the validity of our model.

Low temperature raman study of the electron coherence length near graphene edges.

We developed a novel optical defocusing method for studying spatial coherence of photoexcited electrons and holes near edges of graphene. Our method is applied to measure the localization l(D) of the disorder-induced Raman D band (∼1350 cm(-1)) with a resolution of a few nanometers. Raman scattering experiments performed in a helium bath cryostat reveal that as temperature is decreased from 300 to 1.55 K, the length l(D) increases. We found that the localization of the D band varies as 1/T(1/2), giving strong evidence that l(D) scales with the coherence length of photoexcited electrons near graphene edges.