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 2x10^11 cm-2 for the residual carrier concentration. On the supported regions, significantly higher and spatially inhomogeneous doping is observed. The free-standing graphene monolayers show little local disorder, based on the very weak Raman D-mode response. The two-phonon 2D mode of the free-standing graphene monolayers is downshifted in frequency compared to that of the supported region of the samples and exhibits a narrowed, positively skewed line shape.
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 …
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…
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…
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…
The deformation and fracture behaviour of one-atom-thick mechanically exfoliated graphene has been studied in detail. Monolayer graphene flakes with different lengths, widths and shapes were successfully prepared by mechanical exfoliation and deposited onto poly(methyl methacrylate) (PMMA) beams. The fracture behaviour of the monolayer graphene was followed by deforming the PMMA beams. Through in-situ Raman mapping at different strain levels, the distributions of strain over the graphene flakes were determined from the shift of the graphene Raman 2D band. The failure mechanisms of the exfoliat…
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…
Gold-assisted mechanical exfoliation currently represents a promising method to separate ultra-large (cm-scale) transition metal dichalcogenides (TMDs) monolayers (1L) with excellent electronic and optical properties from the parent van der Waals (vdW) crystals. The strong interaction between $Au$ and chalcogen atoms is the key to achieve this nearly perfect 1L exfoliation yield. On the other hand, it may affect significantly the doping and strain of 1L TMDs in contact with Au. In this paper, we systematically investigated the morphology, strain, doping, and electrical properties of large area…
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…
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…
Raman spectroscopy is a precious tool for the characterization of van der Waals materials, e.g. for the determination of the layer number in thin exfoliated flakes. For sensitive materials, however, this method can be dramatically invasive. In particular, the light intensity required to obtain a significant Raman signal is sufficient to immediately photo-oxidize few-layer thick metallic van der Waals materials. In this work we investigated the impact of the environment on Raman characterization of thin NbSe$_2$ crystals. We show that in ambient conditions the flake is locally oxidized even for…
Low dimensional systems, nanowires, in particular, have exhibited excellent optical and electronic properties. Understanding the thermal properties in semiconductor nanowires is very important for their applications in their electronic devices. In the present study, the thermal conductivity of a freestanding silicon nanowire (NW) is estimated employing the Raman spectroscopy. The advantage of this technique is that the light source (laser) can be used both as heating and excitation source. The variations of the first-order Raman peak position of the freestanding silicon NW with respect to temp…
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…
As the synthesis of graphene on copper became one of the primary preparation methods for both fundamental research and industrial application, Raman spectra of graphene/Cu systems need to be quantitatively understood regarding how their interactions affect the electronic structure of graphene. Using multi-wavelength Raman spectroscopy, we investigated three types of graphene bound on Cu: graphene grown on Cu foils and Cu film/SiO2, and Cu-evaporated exfoliated graphene. 2D peak frequencies of the first two samples were ~17 cm-1 higher than expected for 1.96 eV excitation even when the effect o…
We perform local nanoscale studies of the surface and interface structure of hydrogen intercalated graphene on 4H-SiC(1000). In particular, we show that intercalation of the interfacial layer results in the formation of quasi-free standing one layer graphene (QFS 1LG) with change in the carrier type from n- to p-type, accompanied by a more than four times increase in carrier mobility. We demonstrate that surface enhanced Raman scattering (SERS) reveals the enhanced Raman signal of Si-H stretching mode, which is the direct proof of successful intercalation. Furthermore, the appearance of D, D+D…
III-VI post-transition metal chalcogenides (InSe and GaSe) are a new class of layered semiconductors, which feature a strong variation of size and type of their band gaps as a function of number of layers (N). Here, we investigate exfoliated layers of InSe and GaSe ranging from bulk crystals down to monolayer, encapsulated in hexagonal boron nitride, using Raman spectroscopy. We present the N-dependence of both intralayer vibrations within each atomic layer, as well as of the interlayer shear and layer breathing modes. A linear chain model can be used to describe the evolution of the peak posi…
The Raman exponent of single-molecular magnetic relaxation may take various unexpected values because of rich phonon spectrum and spin-phonon coupling of molecular crystals. We systematically examine the origins of different abnormalities, and clarify misunderstandings in the past, particularly the appropriateness of the fitting procedures for the exponents. We find that exponential laws raised by optical phonons can yield spurious power laws with low exponents. This observation indicates long-standing misunderstandings for origins of low Raman exponents in a large bulk of single-molecule magn…
Raman spectroscopic characterization of stacking configuration and interlayer coupling of twisted multilayer graphene grown by chemical vapor deposition
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…
Electrochemical exfoliation is one of the most promising methods for scalable production of graphene. However, limited understanding of its Raman spectrum as well as lack of measurement standards for graphene strongly limit its industrial applications. In this work we show a systematic study of the Raman spectrum of electrochemically exfoliated graphene, produced using different electrolytes and different types of solvents in varying amounts. We demonstrate that no information on the thickness can be extracted from the shape of the 2D peak as this type of graphene is defective. Furthermore, th…
The quasi-free-standing nature of graphene on H-saturated SiC(0001)
我们报道了在6 H-SiC（0001）上通过在缓冲层下嵌入氢制备的准独立石墨烯的研究。利用红外吸收光谱，我们证明了SiC（0001）表面是饱和的氢。拉曼光谱表明缓冲层转化为石墨烯，石墨烯表现出轻微的拉伸应变和短程缺陷。这些层是空穴掺杂的（p = 5.0-6.5 x 10^12 cm^（-2）），室温下载流子迁移率为3，100 cm ^2/Vs。与缓冲层上的石墨烯相比，对于H-封端的SiC（0001）上的石墨烯，观察到迁移率的温度依赖性大大降低，这证明了术语“准自立”的合理性。
The epitaxial growth of functional materials using a substrate with a graphene layer is a highly desirable method for improving structural quality and obtaining free-standing epitaxial nano-membranes for scientific study, applications, and economical reuse of substrates. However, the aggressive oxidizing conditions typically employed to grow epitaxial perovskite oxides can damage graphene. Here, we demonstrate a technique based on hybrid molecular beam epitaxy that does not require an independent oxygen source to achieve epitaxial growth of complex oxides without damaging the underlying graphe…
Covalently functionalizing mechanical exfoliated monolayer and bilayer graphenides with λ-iodanes led to the discovery that the monolayers supported on a SiO2 substrate are considerably more reactive than bilayers as demonstrated by statistical Raman spectroscopy/microscopy. Supported by DFT calculations we show that ditopic addend binding leads to much more stable products than the corresponding monotopic reactions due to much lower lattice strain of the reactions products. The chemical nature of the substrate (graphene versus SiO2) plays a crucial role.14858-14862.
Two-dimensional (2D) multiferroics are key candidate materials towards advancement of smart technology. Here, we employed a simple synthesis approach to address the long-awaited dream of developing ferroelectric and multiferroic 2D materials, specially in the new class of materials called MXenes. The etched Ti$_3$C$_2$T$_x$ MXene was first synthesized after HF-treatment followed by delamination process for successful synthesis of free-standing Ti$_3$C$_2$T$_x$ film. The free-standing film was then exposed to air at room-temperature as well as heated at different temperature to form TiO$_2$ lay…
Talc is an insulating layered material that is stable at ambient conditions and has high-quality basal cleavage, which is a major advantage for its use in van der Waals heterostructures. Here, we use near-field synchrotron infrared nanospectroscopy, Raman spectroscopy, and first-principles calculations to investigate the structural and vibrational properties of talc crystals, ranging from monolayer to bulk, in the 300-750 cm-1 and <60 cm-1 spectral windows. We observe a symmetry crossover from mono to bilayer talc samples, attributed to the stacking of adjacent layers. The in-plane lattice par…
