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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.

The structural polymorphism intrinsic to select transition metal dichalcogenides provides exciting opportunities for engineering novel devices. Of special interest are memory technologies that rely upon controlled changes in crystal phase, collectively known as phase change memories (PCMs). MoTe$_2$ is ideal for PCMs as the ground state energy difference between the hexagonal (2H, semiconducting) and monoclinic (1T’, metallic) phases is minimal. This energy difference can be made arbitrarily small by substituting W for Mo on the metal sublattice, thus improving PCM performance. Therefore, understanding the properties of Mo$_{1-x}$W$_x$Te$_2$ alloys across the entire compositional range is vital for the technological application of these versatile materials. We combine Raman spectroscopy with aberration-corrected scanning transmission electron microscopy and x-ray diffraction to explore the MoTe$_2$-WTe$_2$ alloy system. The results of these studies enable the construction of the complete alloy phase diagram, while polarization-resolved Raman measurements provide phonon mode and symmetry assignments for all compositions. Temperature-dependent Raman measurements indicate a transition from 1T’-MoTe$_2$ to a distorted orthorhombic phase (T$_d$) below 250 K and facilitate identification of the anharmonic contributions to the optical phonon modes in bulk MoTe$_2$ and Mo$_{1-x}W$_x$Te$_2$ alloys. We also identify a Raman-forbidden MoTe$_2$ mode that is activated by compositional disorder and find that the main WTe$_2$ Raman peak is asymmetric for x

We introduce a simple criterion to identify two-dimensional (2D) materials based on the comparison between experimental lattice constants and lattice constants mainly obtained from Materials-Project (MP) density functional theory (DFT) calculation repository. Specifically, if the relative difference between the two lattice constants for a specific material is greater than or equal to 5%, we predict them to be good candidates for 2D materials. We have predicted at least 1356 such 2D materials. For all the systems satisfying our criterion, we manually create single layer systems and calculate their energetics, structural, electronic, and elastic properties for both the bulk and the single layer cases. Currently the database consists of 1012 bulk and 430 single layer materials, of which 371 systems are common to bulk and single layer. The rest of calculations are underway. To validate our criterion, we calculated the exfoliation energy of the suggested layered materials, and we found that in 88.9% of the cases the currently accepted criterion for exfoliation was satisfied. Also, using molybdenum telluride as a test case, we performed X-ray diffraction and Raman scattering experiments to benchmark our calculations and understand their applicability and limitations. The data is publicly available at the website http://www.ctcms.nist.gov/~knc6/JVASP.html.

We present a new transfer procedure for graphene using acetic acid, which removes the residue that is common in standard acetone treatments. Post-transfer samples cleaned with acetic acid and acetone were characterized using Raman spectroscopy and atomic force microscopy for comparison. We further illustrate the quality of our transfer process by using fluorescence quenching to create an optical map of surface contaminants., 3 pages, 3 figures

Molybdenum ditelluride (MoTe2), which can exist in a semiconducting prismatic hexagonal (2H) or a metallic distorted octahedral (1T') phases, is one of the very few materials that exhibit metal-semiconductor transition. Temperature-driven 2H – 1T’ phase transition in bulk MoTe2 occurs at high temperatures (above ~900 C) and it is usually accompanied by Te loss. The latter can exacerbate the control over reversibility of the phase transition. Here, we study effects of high-temperature annealing on phase transition in MoTe2 single crystals. First, MoTe2 were grown in sealed evacuated quartz ampoules from polycrystalline MoTe2 powder in an iodine-assisted chemical vapor transport process at 1000 C. The 2H and 1T’ phases were stabilized by controlling the cooling rate after the growth. In particular, slow cooling at 10 C/h rate yielded the 2H phase whereas the 1T’ phase was stabilized by ice-water quenching. Next, the phase conversion was achieved by annealing MoTe2 single crystals in vacuum-sealed ampoules at 1000 C with or without additional poly-MoTe2 powder followed by fast or slow cooling. Similarly to the CVT growth, slow cooling and quenching consistently produced 2H and 1T’ phases, respectively, regardless of the initial MoTe2 crystal structure. We will discuss structural and optical properties of the as-grown and phase-converted MoTe2 single crystals using TEM, SEM/EDS, XRD, XPS and Raman. Electrical characteristics of two-terminal devices made from metallic 1T’ and bottom-gated FETs made from 2H exfoliated crystals will also be presented.

We examine anharmonic contributions to the optical phonon modes in bulk $T_d$-MoTe$_2$ through temperature-dependent Raman spectroscopy. At temperatures ranging from 100 K to 200 K, we find that all modes redshift linearly with temperature in agreement with the Gr\"{u}neisen model. However, below 100 K we observe nonlinear temperature-dependent frequency shifts in some modes. We demonstrate that this anharmonic behavior is consistent with the decay of an optical phonon into multiple acoustic phonons. Furthermore, the highest frequency Raman modes show large changes in intensity and linewidth near $T\approx 250$ K that correlate well with the $T_d \to 1T^\prime$ structural phase transition. These results suggest that phonon-phonon interactions can dominate anharmonic contributions at low temperatures in bulk $T_d$-MoTe$_2$, an experimental regime that is currently receiving attention in efforts to understand Weyl semimetals., Comment: 14 pages, 3 figures, 1 table

With a template-stripping fabrication technique, we demonstrate the mass fabrication of high-quality, uniform, ultrasharp (10 nm) metallic probes suitable for single-molecule fluorescence imaging, tip-enhanced Raman spectroscopy (TERS), and other near-field imaging techniques. We achieve reproducible single-molecule imaging with sub-20-nm spatial resolution and an enhancement in the detected fluorescence signal of up to 200. Similar results are obtained for TERS imaging of carbon nanotubes. We show that the large apex angle (70.5°) of our pyramidal tip is well suited to scatter the near-field optical signal into the far-field, leading to larger emission enhancement and hence to a larger quantum yield. Each gold or silver pyramidal probe is used on-demand, one at a time, and the unused tips can be stored for extended times without degradation or contamination. The high yield (>95%), reproducibility, durability, and massively parallel fabrication (1.5 million identical probes over a wafer) of the probes hold promise for reliable optical sensing and detection and for cementing near-field optical imaging and spectroscopy as a routine characterization technique., ACS Nano, 6 (10), ISSN:1936-0851, ISSN:1936-086X

Optical antennas made of gold nanoparticles are used to enhance the spectroscopic response of single molecules. With a scannable optical half-wave antenna in the form of a gold nanorod we achieve a spatial resolution of 20nm in fluorescence imaging. We explore simultaneous fluorescence and Raman enhancement of dye molecules in the junction of two gold nanoparticles and find similar enhancements as a function of interparticle distance for both fluorescence and Raman scattering. We compare our results with theoretical predictions and provide possible explanations.

We study the symmetry properties of 1T' MoTe2 using polarized Raman and second harmonic generation. We find that while the inversion symmetry is broken for even numbers of layers, the Raman modes are nearly unchanged.

Nanocarbon materials, including sp2 hybridized two-dimensional graphene and one-dimensional carbon nanotubes, and sp1 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.

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.

In this article we review Raman studies of defects and dopants in graphene as well as the importance of both for device applications. First a brief overview of Raman spectroscopy of graphene is presented. In the following section we discuss the Raman characterization of three defect types: point defects, edges, and grain boundaries. The next section reviews the dependence of the Raman spectrum on dopants and highlights several common doping techniques. In the final section, several device applications are discussed which exploit doping and defects in graphene. Generally defects degrade the figures of merit for devices, such as carrier mobility and conductivity, whereas doping provides a means to tune the carrier concentration in graphene thereby enabling the engineering of novel material systems. Accurately measuring both the defect density and doping is critical and Raman spectroscopy provides a powerful tool to accomplish this task.

The strain field surrounding a spherical indentation in silicon is mapped in two dimensions (2-D) using electron backscatter diffraction (EBSD) cross-correlation and confocal Raman spectroscopy techniques. The 200 mN indentation created a 4 μm diameter residual contact impression in the silicon (001) surface. Maps about 50 μm × 50 μm area with 128 pixels × 128 pixels were generated in several hours, extending, by comparison, assessment of the accuracy of both techniques to mapping multiaxial strain states in 2-D. EBSD measurements showed a residual strain field dominated by in-surface normal and shear strains, with alternating tensile and compressive lobes extending about three to four indentation diameters from the contact and exhibiting two-fold symmetry. Raman measurements showed a residual Raman shift field, dominated by positive shifts, also extending about three to four indentation diameters from the contact but exhibiting four-fold symmetry. The 2-D EBSD results, in combination with a mechanical-spectroscopic analysis, were used to successfully predict the 2-D Raman shift map in scale, symmetry, and shift magnitude. Both techniques should be useful in enhancing the reliability of microelectromechanical systems (MEMS) through identification of the 2-D strain fields in MEMS devices.

The structural polymorphism in transition metal dichalcogenides (TMDs) provides exciting opportunities for developing advanced electronics. For example, MoTe$_2$ crystallizes in the 2H semiconducting phase at ambient temperature and pressure, but transitions into the 1T$^\prime$ semimetallic phase at high temperatures. Alloying MoTe$_2$ with WTe$_2$ reduces the energy barrier between these two phases, while also allowing access to the T$_d$ Weyl semimetal phase. The MoWTe$_2$ alloy system is therefore promising for developing phase change memory technology. However, achieving this goal necessitates a detailed understanding of the phase composition in the MoTe$_2$-WTe$_2$ system. We combine polarization-resolved Raman spectroscopy with X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) to study MoWTe$_2$ alloys over the full compositional range x from 0 to 1. We identify Raman and XRD signatures characteristic of the 2H, 1T$^\prime$, and T$_d$ structural phases that agree with density-functional theory (DFT) calculations, and use them to identify phase fields in the MoTe$_2$-WTe$_2$ system, including single-phase 2H, 1T$^\prime$, and T$_d$ regions, as well as a two-phase 1T$^\prime$ + T$_d$ region. Disorder arising from compositional fluctuations in MoWTe$_2$ alloys breaks inversion and translational symmetry, leading to the activation of an infrared 1T$^\prime$-MoTe$_2$ mode and the enhancement of a double-resonance Raman process in 2H-MoWTe$_2$ alloys. Compositional fluctuations limit the phonon correlation length, which we estimate by fitting the observed asymmetric Raman lineshapes with a phonon confinement model. These observations reveal the important role of disorder in MoWTe$_2$ alloys, clarify the structural phase boundaries, and provide a foundation for future explorations of phase transitions and electronic phenomena in this system.

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 $\ensuremath{\sim}30\text{ }\text{ }\mathrm{nm}$ for the optical phonons in graphene, the results varying with vibrational symmetries and spatial confinement of the phonons.

A theoretical study describing the coherence properties of near-field Raman scattering in two- and one-dimensional systems is presented. The model is applied to the Raman modes of pristine graphene and graphene edges. Our analysis is based on the tip-enhanced Raman scheme, in which a sharp metal tip located near the sample surface acts as a broadband optical antenna that transfers the information contained in the spatially correlated (but nonpropagating) near field to the far field. The dependence of the scattered signal on the tip-sample separation is explored, and the theory predicts that the signal enhancement depends on the particular symmetry of a vibrational mode. The model can be applied to extract the correlation length Lc of optical phonons from experimentally recorded near-field Raman measurements. The coherence properties of optical phonons have been broadly explored in the time and frequency domains, and the spatially resolved approach presented here provides a complementary methodology for the study of local material properties at the nanoscale., Physical Review X, 4 (3), ISSN:2160-3308

We optically determine the thickness of molybdenum disulfide (MoS2) flakes by photoluminescence and Raman measurements. A transfer technique is demonstrated to pick and place MoS2 flakes on target structures.

A theory describing the near-field Raman enhancement in two-dimensional (2D) systems is presented. The analysis quantifies the near-field Raman intensity as a function of the tip-sample distance, Raman polarizability tensor components, incident laser beam configuration, and tip orientation relative to the sample plane. Our results show that the near-field Raman intensity is inversely proportional to the 10th and 8th power of the tip-sample distance in the incoherent and coherent scattering regimes, respectively. Optimal conditions for the tip inclination angle for different configurations are determined, and the results can be used as a guide for tip-enhanced Raman spectroscopy (TERS) experiments in 2D systems such as graphene, two-dimensional electron gases, and topological insulators.

We demonstrate using reproducible, mass fabricated metallic microstructures as near-field optical probes for fluorescence and Raman spectroscopy. We observe fluorescent rate enhancement up to 200-fold and sub-20 nm spatial resolution.

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.

This paper reports the experimental determination of the phase-breaking length L of conduction electrons in graphene using Raman spectroscopy. Based on the double-resonance model, we extract L from the spatial dependence of the D band susceptibility near the graphene edge. By using prior knowledge of sample properties and the excitation point-spread function we are able to determine the spatial variation of the Raman susceptibilities with high accuracy, and the results reveal a phase-breaking length L~40nm near the graphene edge., 5 pages, 2 figures