Enhanced Raman and photoluminescence response in monolayer MoS2_2 due to laser healing of defects

Bound quasiparticles, negatively charged trions and neutral excitons, are associated with the direct optical transitions at the K-points of the Brillouin zone for monolayer MoS$_2$. The change in the carrier concentration, surrounding dielectric constant and defect concentration can modulate the photoluminescence and Raman spectra. Here we show that exposing the monolayer MoS$_2$ in air to a modest laser intensity for a brief period of time enhances simultaneously the photoluminescence (PL) intensity associated with both trions and excitons, together with $\sim$ 3 to 5 times increase of the Raman intensity of first and second order modes. The simultaneous increase of PL from trions and excitons cannot be understood based only on known-scenario of depletion of electron concentration in MoS$_2$ by adsorption of O$_2$ and H$_2$O molecules. This is explained by laser induced healing of defect states resulting in reduction of non-radiative Auger processes. This laser healing is corroborated by an observed increase of intensity of both the first order and second order 2LA(M) Raman modes by a factor of $\sim$ 3 to 5. The A$_{1g}$ mode hardens by $\sim$ 1.4 cm$^{-1}$ whereas the E$^1_{2g}$ mode softens by $\sim$ 1 cm$^{-1}$. The second order 2LA(M) Raman mode at $\sim$ 440 cm$^{-1}$ shows an increase in wavenumber by $\sim$ 8 cm$^{-1}$ with laser exposure. These changes are a combined effect of change in electron concentrations and oxygen-induced lattice displacements.Comment: 15 pages, 5 figures, Journal of Raman Spectroscopy, 201

Phonon Anomalies, Orbital-Ordering and Electronic Raman Scattering in iron-pnictide Ca(Fe0.97Co0.03)2As2: Temperature-dependent Raman Study

We report inelastic light scattering studies on Ca(Fe0.97Co0.03)2As2 in a wide spectral range of 120-5200 cm-1 from 5K to 300K, covering the tetragonal to orthorhombic structural transition as well as magnetic transition at Tsm ~ 160K. The mode frequencies of two first-order Raman modes B1g and Eg, both involving displacement of Fe atoms, show sharp increase below Tsm. Concomitantly, the linewidths of all the first-order Raman modes show anomalous broadening below Tsm, attributed to strong spin-phonon coupling. The high frequency modes observed between 400-1200 cm-1 are attributed to the electronic Raman scattering involving the crystal field levels of d-orbitals of Fe2+. The splitting between xz and yz d-orbital levels is shown to be ~ 25 meV which increases as temperature decreases below Tsm. A broad Raman band observed at ~ 3200 cm-1 is assigned to two-magnon excitation of the itinerant Fe 3d antiferromagnet.Comment: Accepted for Publication in JPC

Symmetry-dependent phonon renormalization in monolayer MoS2 transistor

Strong electron-phonon interaction which limits electronic mobility of semiconductors can also have significant effects on phonon frequencies. The latter is the key to the use of Raman spectroscopy for nondestructive characterization of doping in graphene-based devices. Using in-situ Raman scattering from single layer MoS$_2$ electrochemically top-gated field effect transistor (FET), we show softening and broadening of A$_{1g}$ phonon with electron doping whereas the other Raman active E$_{2g}^{1}$ mode remains essentially inert. Confirming these results with first-principles density functional theory based calculations, we use group theoretical arguments to explain why A$_{1g}$ mode specifically exhibits a strong sensitivity to electron doping. Our work opens up the use of Raman spectroscopy in probing the level of doping in single layer MoS$_2$-based FETs, which have a high on-off ratio and are of enormous technological significance.Comment: 5 pages, 3 figure

Metallic monoclinic phase in VO2_2 induced by electrochemical gating: in-situ Raman study

We report in-situ Raman scattering studies of electrochemically top gated VO$_2$ thin film to address metal-insulator transition (MIT) under gating. The room temperature monoclinic insulating phase goes to metallic state at a gate voltage of 2.6 V. However, the number of Raman modes do not change with electrolyte gating showing that the metallic phase is still monoclinic. The high frequency Raman mode A$_g$(7) near 616 cm$^{-1}$ ascribed to V-O vibration of bond length 2.06 \AA~ in VO$_6$ octahedra hardens with increasing gate voltage and the B$_g$(3) mode near 654 cm$^{-1}$ softens. This shows that the distortion of the VO$_6$ octahedra in the monoclinic phase decreases with gating. The time dependent Raman data at fixed gate voltages of 1 V (for 50 minute, showing enhancement of conductivity by a factor of 50) and 2 V (for 130 minute, showing further increase in conductivity by a factor of 5) show similar changes in high frequency Raman modes A$_g$(7) and B$_g$(3) as observed in gating. This slow change in conductance together with Raman frequency changes show that the governing mechanism for metalization is more likely to the diffusion controlled oxygen vacancy formation due to the applied electric field.Comment: 5 pages, 6 figure

Sharp Raman Anomalies and Broken Adiabaticity at a Pressure Induced Transition from Band to Topological Insulator in Sb2Se3

The nontrivial electronic topology of a topological insulator is thus far known to display signatures in a robust metallic state at the surface. Here, we establish vibrational anomalies in Raman spectra of the bulk that signify changes in electronic topology: an E2 g phonon softens unusually and its linewidth exhibits an asymmetric peak at the pressure induced electronic topological transition (ETT) in Sb2Se3 crystal. Our first-principles calculations confirm the electronic transition from band to topological insulating state with reversal of parity of electronic bands passing through a metallic state at the ETT, but do not capture the phonon anomalies which involve breakdown of adiabatic approximation due to strongly coupled dynamics of phonons and electrons. Treating this within a four-band model of topological insulators, we elucidate how nonadiabatic renormalization of phonons constitutes readily measurable bulk signatures of an ETT, which will facilitate efforts to develop topological insulators by modifying a band insulator

Ultra thin films of nanocrystalline Ge studied by AFM and interference enhanced Raman scattering

Initial growth stages of the ultra thin films of germanium (Ge) prepared by ion beam sputter deposition have been studied using atomic force microscope (AFM) and interference enhanced Raman scattering. The growth of the films follows Volmer-Weber growth mechanism. Analysis of the AFM images shows that Ostwald ripening of the grains occurs as the thickness of the film increases. Raman spectra of the Ge films reveal phonon confinement along the growth direction and show that the misfit strain is relieved for film thickness greater than 4 nm

Raman anomalies as signatures of pressure induced electronic topological and structural transitions in black phosphorus: Experiments and Theory

We report high pressure Raman experiments of Black phosphorus up to 24 GPa. The line widths of first order Raman modes A$^1_g$, B$_{2g}$ and A$^2_g$ of the orthorhombic phase show a minimum at 1.1 GPa. Our first-principles density functional analysis reveals that this is associated with the anomalies in electron-phonon coupling at the semiconductor to topological insulator transition through inversion of valence and conduction bands marking a change from trivial to nontrivial electronic topology. The frequencies of B$_{2g}$ and A$^2_g$ modes become anomalous in the rhombohedral phase at 7.4 GPa, and new modes appearing in the rhombohedral phase show anomalous softening with pressure. This is shown to originate from unusual structural evolution of black phosphorous with pressure, based on first-principles theoretical analysis.Comment: 13pages, 12figure

Anomalous Raman scattering from phonons and electrons of superconducting FeSe0.82_{0.82}

We report interesting anomalies in the temperature dependent Raman spectra of FeSe$_{0.82}$ measured from 3K to 300K in the spectral range from 60 to 1800 cm$^{-1}$ and determine their origin using complementary first-principles density functional calculations. A phonon mode near 100 cm$^{-1}$ exhibits a sharp increase by $\sim$ 5% in frequency below a temperature T$_s$ ($\sim$ 100 K) attributed to strong spin-phonon coupling and onset of short-range antiferromagnetic order. In addition, two high frequency modes are observed at 1350 cm$^{-1}$ and 1600 cm$^{-1}$, attributed to electronic Raman scattering from ($x^2-y^2$)to $xz$ / $yz$ $d$-orbitals of Fe.Comment: 19 pages, 4 figures, 1 tabl

Raman Signatures of Strong Kitaev Exchange Correlations in (Na1−x_{1-x}Lix_x)2_2IrO3_3 : Experiments and Theory

Inelastic light scattering studies on single crystals of (Na$_{1-x}$Li$_x$)$_2$IrO$_3$ ($x = 0, 0.05$ and $0.15$) show a polarization independent broad band at $\sim$~2750 cm$^{-1}$ with a large band-width $\sim 1800$~cm$^{-1}$. For Na$_2$IrO$_3$ the broad band is seen for temperatures $\leq 200$~K and persists inside the magnetically ordered state. For Li doped samples, the intensity of this mode increases, shifts to lower wave-numbers and persists to higher temperatures. Such a mode has recently been predicted (Knolle et.al.) as a signature of the Kitaev spin liquid. We assign the observation of the broad band to be a signature of strong Kitaev-exchange correlations. The fact that the broad band persists even inside the magnetically ordered state suggests that dynamically fluctuating moments survive even below $T_{N}$. This is further supported by our mean field calculations. The Raman response calculated in mean field theory shows that the broad band predicted for the spin liquid state survives in the magnetically ordered state near the zigzag-spin liquid phase boundary. A comparison with the theoretical model gives an estimate of the Kitaev exchange interaction parameter to be $J_K\approx 57$~meV.Comment: 14pages 4 figure

Electron-Hole Asymmetry in the Electron-phonon Coupling in Top-gated Phosphorene Transistor

Using in-situ Raman scattering from phosphorene channel in an electrochemically top-gated field effect transistor, we show that its phonons with A$_g$ symmetry depend much more strongly on concentration of electrons than that of holes, while the phonons with B$_g$ symmetry are insensitive to doping. With first-principles theoretical analysis, we show that the observed electon-hole asymmetry arises from the radically different constitution of its conduction and valence bands involving $\pi$ and $\sigma$ bonding states respectively, whose symmetry permits coupling with only the phonons that preserve the lattice symmetry. Thus, Raman spectroscopy is a non-invasive tool for measuring electron concentration in phosphorene-based nanoelectronic devices