Detailed high pressure Resonance Raman ($RR$) Spectroscopy and X-ray diffraction ($XRD$) studies are carried out on 3-4 layered $MoSe_2$ obtained by liquid exfoliation. Analysis of ambient $XRD$ pattern and $RR$ spectra indicate the presence of a triclinic phase along with its parent hexagonal phase. Pressure evolution of prominent Raman modes and their full width at half maximum ($FWHM$) show slope changes at about 13 GPa and 33 GPa, respectively. Slope change in the linear behavior of reduced pressure ($H$) with respect to Eulerian strain ($f_E$) is observed at about 13 GPa. A minimum in the $FWHM$ values of $E_{2g}^1$ and $A_{2u}^2$ modes at the same pressure indicate to an electronic topological transition ($ETT$). Above 33 GPa the sample completely gets converted to the triclinic structure, which indicates the importance of strain in structural as well as electronic properties of two dimensional materials.
The excitonic homogeneous linewidth of an exfoliated monolayer MoSe$_2$ encapsulated in hexagonal boron nitride is directly measured using multidimensional coherent spectroscopy with micron spatial resolution. The linewidth is 0.26 $\pm$ 0.02 meV, corresponding to a dephasing time $T_2 \approx$ 2.5 ps, which is almost half the narrowest reported values for non-encapsulated MoSe$_2$ flakes. We attribute the narrowed linewidth to Coulomb screening by the encapsulated material and suppression of non-radiative processes. Through direct measurements of encapsulated and non-encapsulated monolayers, …
Janus monolayer transition metal dichalcogenides, where one of the two chalcogen layers is substituted with a different kind of chalcogen atoms, are pushing the properties of two dimensional materials into new territories. Yet only little is known about this new kind of material class, mainly due to the challenging synthesis. In this work we propose a method to prepare high quality Janus MoSSe monolayers from as-exfoliated MoSe2 by thermal sulfurization. With this we aim to pave a way for more exotic Janus monolayers, which have been out of the experimental reach thus far. The synthesized MoSS…
2H-TaSe2 is a model transition metal dichalcogenide material that develops charge density waves (CDWs).Here we present variable-temperature Raman spectroscopy study on both incommensurate charge density waves (ICDW) and optical phonon modes of 2H-TaSe2 thin layers exfoliated onto SiO2 substrate. Raman scattering intensities of all modes reach a maximum when the sample thickness is about 11 nm. This phenomenon can be explained by optical interference effect between the sample and the substrate. The E2gICDW amplitude modes experience redshift as temperature increases. We extract ICDW transition …
The properties of pristine, free-standing graphene monolayers prepared by mechanical exfoliation of graphite are investigated. The graphene monolayers, suspended over open trenches, are examined by means of spatially resolved Raman spectroscopy of the G-, D-, and 2D-phonon modes. The G-mode phonons exhibit reduced energies (1580 cm-1) and increased widths (14 cm-1) compared to the response of graphene monolayers supported on the SiO2 covered substrate. From analysis of the G-mode Raman spectra, we deduce that the free-standing graphene monolayers are essentially undoped, with an upper bound of…
We investigate the thermal properties of these Zirconium based materials using confocal Raman spectroscopy. We observed 2 different and distinctive Raman signatures for exfoliated ZrX2 (where X = S or Se). These Raman modes generally depend on the shape of the exfoliated nanosheets, regardless of the incident laser polarization. These 2 shapes are divided into 2D- ZrX2 and quasi 1D- ZrX2. For 2D- ZrX2, Raman modes are in alignment with those reported in literature. However, for quasi 1D-ZrX2, we show that Raman modes are identical to exfoliated ZrX3 nanosheets, indicating a major lattice trans…
Bismuth telluride - Bi(2)Te(3)- and related compounds have recently attracted strong interest owing to the discovery of the topological insulator properties in many members of this family of materials. The few-quintuple films of these materials are particularly interesting from the physics point of view. We report results of the micro-Raman spectroscopy study of the "graphene-like" exfoliated few-quintuple layers of Bi(2)Te(3), Bi(2)Se(3) and Sb(2)Te(3). It is found that crystal symmetry breaking in few-quintuple films results in appearance of A1u-symmetry Raman peaks, which are not active in …
Resonance Raman scattering, which probes electrons, phonons and their interplay in crystals, is extensively used in two-dimensional materials. Here we investigate Raman modes in MoSe$_2$ at different laser excitation energies from 2.33 eV down to the near infrared 1.16 eV. The Raman spectrum at 1.16 eV excitation energy shows that the intensity of high-order modes is strongly enhanced if compared to the first-order phonon modes intensity due to resonance effects with the MoSe$_2$ indirect band gap. By comparing the experimental results with the two-phonon density of states calculated with dens…
Raman investigation of MoSe2 was carried out with eight different excitation energies. Seven peaks, including E1g, A1g, E2g1, and A2u2 peaks are observed in the range of 100-400 cm-1. The phonon modes are assigned by comparing the peak positions with theoretical calculations. The intensities of the peaks are enhanced at different excitation energies through resonance with different optical transitions. The A1g mode is enhanced at 1.58 and 3.82 eV, which are near the A exciton energy and the band-to-band transition between higher energy bands, respectively. The E2g1 mode is strongly enhanced wi…
Defects play a significant role in optical properties of semiconducting two-dimensional transition metal dichalcogenides (TMDCs). In ultra-thin MoSe2, a remarkable feature at ~250 cm-1 in Raman spectra is ascribed to be a defect-related mode. Recent attempts failed to explain the origin of this peak, leaving it being a mystery. Here in this work, we demonstrate that this peak is a Se vacancy induced defect mode. Heat effect and hydrogen etching are two main factors to introduce Se vacancies in CVD process of growing MoSe2. A phonon confinement model can well explain the behaviors of intrinsic …
High surface area graphene sheets were obtained by electrochemical exfoliation of graphite in an acid media under constant potential conditions. Filtration and centrifugation processes played an important role in order to obtain stable dispersions in water. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) imaging revealed highly exfoliated crystalline samples of ~5(\mum). Raman, FT-IR and XPS spectroscopy further confirmed the high quality of the exfoliated material. The electrochemically exfoliated graphene (EEG) was decorated with gold nanoparticles (AuNP) using …
Chemically and mechanically exfoliated MoS$_2$ single-layer samples have substantially different properties. While mechanically exfoliated single-layers are mono-phase (1H polytype with Mo in trigonal prismatic coordination), the chemically exfoliated samples show coexistence of three different phases, 1H, 1T (Mo in octahedral coordination) and 1T$^{'}$ (a distorted $2\times 1$ 1T-superstructure). By using first-principles calculations, we investigate the energetics and the dynamical stability of the three phases. We show that the 1H phase is the most stable one, while the metallic 1T phase, s…
Transition metal dichalcogenides (TMDCs) have attracted significant attention for optoelectronic, photovoltaic and photoelectrochemical applications. The properties of TMDCs are highly dependent on the number of stacked atomic layers, which is usually counted post-fabrication, using a combination of optical methods and atomic force microscopy (AFM) height measurements. Here, we use photoluminescence spectroscopy and three different AFM methods to demonstrate significant discrepancies in height measurements of exfoliated MoSe$_2$ flakes on SiO$_2$ depending on the method used. We highlight that…
We report on the phonon and thermal properties of thin films of tantalum diselenide (2H-TaSe2) obtained via the graphene-like mechanical exfoliation of crystals grown by chemical vapor transport. The ratio of the intensities of the Raman peak from the Si substrate and the E2g peak of TaSe2 presents a convenient metric for quantifying film thickness. The temperature coefficients for two main Raman peaks, A1g and E2g, are -0.013 and -0.0097 cm-1/oC, respectively. The Raman optothermal measurements indicate that the room temperature thermal conductivity in these films decreases from its bulk valu…
Probing phonons, quasi-particle excitations and their coupling has enriched our understanding of these 2D materials and proved to be crucial for developing their potential applications. Here, we report comprehensive temperature, 4-330 K, and polarization-dependent Raman measurements on mono and bilayer MoSe2. Phonon's modes up to fourth-order are observed including forbidden Raman and IR modes, understood considering Frohlich mechanism of exciton-phonon coupling. Most notably, anomalous variations in the phonon linewidths with temperature pointed at the significant role of electron-phonon coup…
Chemical exfoliation of MoS$_2$ via Li-intercalation route has led to many desirable properties and spectacular applications due to the presence of a metastable state in addition to the stable H phase. However, the nature of the specific metastable phase formed, and its basic charge conduction properties have remained controversial. Using spatially resolved Raman spectroscopy (~1 micrometer resolution) and photoelectron spectroscopy (~120 nm resolution), we probe such chemically exfoliated MoS$_2$ samples in comparison to a mechanically exfoliated H phase sample and confirm that the dominant m…
The emerging Au-assisted exfoliation technique provides a wealth of large-area and high-quality ultrathin two-dimensional (2D) materials compared with traditional tape-based exfoliation. Fast, damage-free, and reliable determination of the layer number of such 2D films is essential to study layer-dependent physics and promote device applications. Here, an optical method has been developed for simple, high throughput, and accurate determination of the layer number for Au-assisted exfoliated MoS$_2$ and WS$_2$ films in a broad thickness range. The method is based on quantitative analysis of laye…
Orhorhombic $α$-MoO$_3$ is a layered oxide with various applications and with excellent potential to be exfoliated as a 2D ultrathin film or monolayer. In this paper, we present a first-principles computational study of its vibrational properties. Our focus is on the zone center modes which can be measured by a combination of infared and Raman spectroscopy. The polarization dependent spectra are simulated. Calculations are also performed for a monolayer form in which "double layers" of Mo$_2$O$_6$ which are weakly van der Waals bonded in the $α$-structure are isolated. Shift in phonon frequenc…
MoS_2 in its two-dimensional (2D) form is known to exhibit many fundamentally interesting and technologically important properties. One of the most popular routes to form extensive amount of such 2D samples is the chemical exfoliation route. However, the nature and origin of the specific polymorph of MoS_2 primarily responsible for such spectacular properties has remained controversial with claims of both T and T' phases as well as metallic and semiconducting natures. We show that a comprehensive scrutiny of the available literature data of Raman spectra from such samples allow little scope fo…
The discovery of new families of exfoliatable 2D crystals that have diverse sets of electronic, optical, and spin-orbit coupling properties, enables the realization of unique physical phenomena in these few-atom thick building blocks and in proximity to other materials. Herein, using NaSn2As2 as a model system, we demonstrate that layered Zintl phases having the stoichiometry ATt2Pn2 (A = Group 1 or 2 element, Tt = Group 14 tetrel element and Pn = Group 15 pnictogen element) and feature networks separated by van der Waals gaps can be readily exfoliated with both mechanical and liquid-phase met…
Intercalation offers a promising way to alter the physical properties of two-dimensional (2D) layered materials. Here we investigate the electronic and vibrational properties of 2D layered MoSe$_2$ intercalated with atomic manganese at ambient and high pressure up to 7 GPa by Raman scattering and electronic structure calculations. The behavior of optical phonons is studied experimentally with a diamond anvil cell and computationally through density functional theory calculations. Experiment and theory show excellent agreement in optical phonon behavior. The previously Raman inactive A$_{2u}$ m…
We study the vibrational, magnetic and transport properties of Few Layer Graphene (FLG) using Raman and electron spin resonance spectroscopy and microwave conductivity measurements. FLG samples were produced using wet chemical exfoliation with different post-processing, namely ultrasound treatment, shear mixing, and magnetic stirring. Raman spectroscopy shows a low intensity D mode which attests a high sample quality. The G mode is present at $1580$ cm$^{-1}$ as expected for graphene. The 2D mode consists of 2 components with varying intensities among the different samples. This is assigned to…
We investigated interlayer phonon modes of mechanically exfoliated few-layer 2H-SnS2 samples by using room temperature low-frequency micro-Raman spectroscopy. Raman measurements were performed using laser wavelength of 441.6, 514.4, 532 and 632.8 nm with power below 100 uW and inside a vacuum chamber to avoid photo-oxidation. The intralayer Eg and A1g modes are observed at ~206 cm-1 and ~314 cm-1, respectively, but the Eg mode is much weaker for all excitation energies. The A1g mode exhibits strong resonant enhancement for the 532 nm (2.33 eV) laser. In the low-frequency region, interlayer vib…
Liquid-phase exfoliation is one of the most promising routes for large scale production of multilayer graphene dispersions. These dispersions, which may be used in coatings, composites or paints, are believed to contain disorder-free graphene multilayers. Here we address the nature of defects in such samples obtained by liquid-phase exfoliation of graphite powder in N-methyl--2--pyrrolidone. Our Raman spectroscopy data challenges the assumption that these multilayers are free of bulk defects, revealing that defect localization strongly depends on the sonication time. For short ultrasound times…
We report high pressure X-ray diffraction and a detailed systematic Raman measurements on $ReS_2$ sample, which is mechanically exfoliated from a single crystal. A few new Bragg peaks are observed to emerge above 6 GPa indicating a structural transition from distorted $1T$ to distorted $1T$$^{\prime}$ in triclinic structure. The same is corroborated by appearance of new Raman modes in the same pressure range. Softening of the Raman modes corresponding to $Re$ atom vibrations are observed in the distorted $1T$$^{\prime}$ phase in the pressure range 15-25 GPa. In the same pressure range the anom…
We have investigated antidot lattices, which were prepared on exfoliated graphene single layers via electron-beam lithography and ion etching, by means of scanning Raman spectroscopy. The peak positions, peak widths and intensities of the characteristic phonon modes of the carbon lattice have been studied systematically in a series of samples. In the patterned samples, we found a systematic stiffening of the G band mode, accompanied by a line narrowing, while the 2D mode energies are found to be linearly correlated with the G mode energies. We interpret this as evidence for p-type doping of th…
We report results of micro-Raman spectroscopy investigation of the "graphene-like" mechanically exfoliated single-crystal bismuth telluride films with the thickness ranging from a few-nm-range to bulk limit. It is found that the optical phonon mode A1u, which is not-Raman active in bulk bismuth telluride crystals, appears in the atomically-thin films due to crystal-symmetry breaking. The intensity ratios of the out-of-plane A1u and A1g modes to the in-plane Eg mode grow with decreasing film thickness. The evolution of Raman signatures with the film thickness can be used for identification of b…
A trigonal phase existing only as small patches on chemically exfoliated few layer, thermodynamically stable 1H phase of MoS2 is believed to influence critically properties of MoS2 based devices. This phase has been most often attributed to the metallic 1T phase. We investigate the electronic structure of chemically exfoliated MoS2 few layered systems using spatially resolved (lesser than 120 nm resolution) photoemission spectroscopy and Raman spectroscopy in conjunction with state-of-the-art electronic structure calculations. On the basis of these results, we establish that the ground state o…
We report on room-temperature Raman scattering measurements in few-layer crystals of exfoliated molybdenum ditelluride (MoTe$_{2}$) performed with the use of 632.8 nm (1.96 eV) laser light excitation. In agreement with recent study reported by G. Froehlicher et al, (2015 $Nano$ $Lett.$ 15 6481) we observe a complex structure of the out-of-plane vibrational modes (A$_{1g}$/A$^{'}_{1}$), which can be explained in terms of interlayer interactions between single atomic planes of MoTe$_{2}$. In the case of low-energy shear and breathing modes of rigid interlayer vibrations it is shown that their en…
Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterizat…
2D layered materials have recently attracted tremendous interest due to their fascinating properties and potential applications. The interlayer interactions are much weaker than the intralayer bonds, allowing the as-synthesized materials to exhibit different stacking sequences (e.g. ABAB, ABCABC), leading to different physical properties. Here, we show that regardless of the space group of the 2D material, the Raman frequencies of the interlayer shear modes observed under the typical configuration blue shift for AB stacked materials, and red shift for ABC stacked materials, as the number of la…
Molybdenum disulfide (MoS2) of single and few-layer thickness was exfoliated on SiO2/Si substrate and characterized by Raman spectroscopy. The number of S-Mo-S layers of the samples was independently determined by contact-mode atomic-force microscopy. Two Raman modes, E12g and A1g, exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be expl…
In this paper we demonstrated the thermal Atomic Layer Deposition (ALD) growth at 250 °C of highly homogeneous and ultra-thin ($\approx$ 3.6 nm) $Al_2O_3$ films with excellent insulating properties directly onto a monolayer (1L) $MoS_2$ membrane exfoliated on gold. Differently than in the case of 1L $MoS_2$ supported by a common insulating substrate ($Al_2O_3/Si$), a better nucleation process of the high-k film was observed on the 1L $MoS_2/Au$ system since the ALD early stages. Atomic force microscopy analyses showed a $\approx 50\%$ $Al_2O_3$ surface coverage just after 10 ALD cycles, its in…
We report a comparative study of rigid layer Raman-active modes in $N$-layer transition metal dichalcogenides. Trigonal prismatic (2Hc, such as MoSe$_2$, MoTe$_2$, WS$_2$, WSe$_2$) and distorted octahedral (1T', such as ReS$_2$ and ReSe$_2$) phases are considered. The Raman-active in-plane interlayer shear modes and out-of-plane interlayer breathing modes appear as well-defined features with wavenumbers in the range 0-40~cm$^{-1}$. These rigid layer modes are well-described by an elementary linear chain model from which the interlayer force constants are readily extracted. Remarkably, these fo…
Titanium trisulfide (TiS3) has recently attracted the interest of the 2D community as it presents a direct bandgap of ~1.0 eV, shows remarkable photoresponse, and has a predicted carrier mobility up to 10000 cm2V-1 s-1. However, a study of the vibrational properties of TiS3, relevant to understanding the electron-phonon interaction which can be the main mechanism limiting the charge carrier mobility, is still lacking. In this work, we take the first steps to study the vibrational properties of TiS3 through temperature dependent Raman spectroscopy measurements of TiS3 nanoribbons and nanosheets…
We investigate the interlayer phonon modes in $N$-layer rhenium diselenide (ReSe$_2$) and rhenium disulfide (ReS$_2$) by means of ultralow-frequency micro-Raman spectroscopy. These transition metal dichalcogenides exhibit a stable distorted octahedral (1T') phase with significant in-plane anisotropy, leading to sizable splitting of the (in-plane) layer shear modes. The fan-diagrams associated with the measured frequencies of the interlayer shear modes and the (out-of-plane) interlayer breathing modes are perfectly described by a finite linear chain model and allow the determination of the inte…
Exfoliated chromium triiodide (CrI$_3$) is a layered van der Waals (vdW) magnetic insulator that consists of ferromagnetic layers coupled through antiferromagnetic interlayer exchange. The resulting permutations of magnetic configurations combined with the underlying crystal symmetry produces tunable magneto-optical phenomena that is unique to the two-dimensional (2D) limit. Here, we report the direct observation of 2D magnons through magneto-Raman spectroscopy with optical selection rules that are strictly determined by the honeycomb lattice and magnetic states of atomically thin CrI$_3$. In …
Molybdenum Disulphide (MoS2) is an interesting material which exists in atomically thin multilayers and can be exfoliated into monolayer or a few layers for multiple applications. It has emerged as a promising material for development of such efficient sensors. Here, we have exfoliated and decorated MoS2 flakes with novel, single phase High Entropy Alloy (HEA) nanoparticles using facile and scalable cryomilling technique, followed by sonochemical method. It is found that the decoration of HEA nanoparticles impart surface enhanced Raman scattering effect and reduction in the work function of th…
The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes withrespect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow-frequencies. A wealth of Raman bands is distinguished in the range from 15-150 c…
The use of simple, fast and economic experimental tools to characterize low-dimensional materials is an important step in the process of democratizing the use of such materials in laboratories around the world. Raman spectroscopy has arisen as a way of indirectly determining the thickness of nanolayers of transition metal dichalcogenides (TMDs), avoiding the use of more expensive tools such as atomic force microscopy, and it is therefore a widely used technique in the study of semiconducting TMDs. However, the study of many metallic TMDs in the limit of few atomic layers is still behind when c…
