The elastic component of anisotropic strain dominates the observed shift in the F2g Raman mode of anelastic ceria thin films.

Raman spectroscopy is applied for non-destructive characterization of strain in crystalline thin films. The analysis makes use of the numerical value of the mode Grüneisen parameter γ, which relates the fractional change in the frequency of a Raman-active vibrational mode and the strain-induced fractional change in the unit cell volume. When in-plane, compressive biaxial strain in aliovalent doped CeO2-films is relieved by partial substrate removal, the films exhibit values of γ for the F2g vibrational mode which are ∼30% of the literature values for bulk ceramics under isostatic stress. This discrepancy has been attributed to a negative contribution from the anelastic (time-dependent) mechanical properties of aliovalent-doped ceria. Here we propose a way to "separate" anelastic and elastic contributions to the F2g mode Grüneisen parameter. Mechanically elastic yttria (Y2O3) films on Ti/SiO2/Si substrate serve as "control". The values of γ calculated from the change in frequency of the ∼375 cm-1 F2g Raman-active mode are close to the literature values for bulk yttria under isostatic stress. This work should serve to provide a protocol for characterization of selective sensitivity to different strain components of doped ceria thin films.

Raman scattering from single WS2 nanotubes in stretched PVDF electrospun fibers.

Inorganic WS2 nanotubes (INT-WS2) were embedded into sub-µm polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) electrospun fibers. In this report we explore the Raman scattering spectroscopy from a single nanotube during stretching of individual nanocomposite fibers. Red shifts of up to ∼4.7 cm-1 for A1g and E WS2 bands were found before reaching the "tearing point" of the fibers. These shifts may correlate with up to ∼2.8% of the WS2 nanotube elongation. Moreover, the absence of the A1g and E bands' broadening, as well as the nonappearance of the E shear mode in the nanotube Raman spectra, suggest the stretching of the nanotubes as a whole (including inner layers). These results point to the excellent adhesion of the nanotubes' surface to the polymer and to the effective load transfer from the polymer to the WS2 nanotube. In order to elucidate the nature of interaction between the polymer and the nanofiller, we modeled the deformation of composite fibers using an elastic lattice spring model (LSM). The results of the model are fully consistent with our interpretation.

Direct measurement of band edge discontinuity in individual core-shell nanowires by photocurrent spectroscopy.

Group III-V coaxial core-shell semiconducting nanowire heterostructures possess unique advantages over their planar counterparts in logic, photovoltaic, and light-emitting devices. Dimensional confinement of electronic carriers and interface complexity in nanowires are known to produce local electronic potential landscapes along the radial direction that deviate from those along the normal to planar heterojunction interfaces. However, understanding of selected electronic and optoelectronic carrier transport properties and device characteristics remains lacking without a direct measurement of band alignment in individual nanowires. Here, we report on, in the GaAs/AlxGa1-xAs and GaAs/AlAs core-shell nanowire systems, how photocurrent and photoluminescence spectroscopies can be used together to construct a band diagram of an individual heterostructure nanowire with high spectral resolution, enabling quantification of conduction band offsets.

Cerium metal oxidation studied by IR reflection-absorption and Raman scattering spectroscopies.

Oxidation of cerium metal is a complex process which is strongly affected by the presence of water vapor in the oxidative atmosphere. Here, we explore, by means of infrared reflection-absorption spectroscopy (IRRAS) and Raman scattering spectroscopies, thin oxide films, formed on cerium metal during oxidation, under dry vs ambient (humid) air conditions (∼0.2% and ∼50% relative humidities, respectively) and compare them with a thin film of CeO2deposited on a Si substrate. Complementary analysis of the thin films using x-ray diffraction and focused ion beam-scanning electron microscopy enables the correlation between their structure and spectroscopic characterizations. The initial oxidation of cerium metal results in the formation of highly sub-stoichiometric CeO2-x. Under dry air conditions, a major fraction of that oxide reacts with oxygen to form CeO∼2, which is spectroscopically detected by Raman scatteringF2gsymmetry mode and by IRAASF1usymmetry mode, splitted into doubly-degenerate transverse optic and mono-degenerate longitudinally optic (LO) modes. In contrast, under ambient (humid) conditions, the oxide formed is more heterogenous, as the reaction of CeO2-xdiverges towards the dominant formation of Ce(OH)3. Prior to the spectral emergence of Ce(OH)3, hydrogen ions incorporate into the highly sub-stoichiometric oxide, as manifested by Ce-H local vibrational mode detected in the Raman spectrum. The spectroscopic response of the thin oxide layer thus formed is more complex; particularly noted is the absence of the LO mode. It is attributed to the high density of microstructural and compositional defects in the oxide layer, which results in a heterogenous dielectric nature of the thin film, far from being representable by a single phase of CeO∼2.

Solving the "MoS2 Nanotubes" Synthetic Enigma and Elucidating the Route for Their Catalyst-Free and Scalable Production.

This study solves a more than two-decades-long "MoS2 Nanotubes" synthetic enigma: the futile attempts to synthesize inorganic nanotubes (INTs) of MoS2 via vapor-gas-solid (VGS) reaction. Among them was replication of the recently reported pure-phase synthesis of the analogous INT-WS2. During these years, successful syntheses of spherical nanoparticles of WS2 and MoS2 were demonstrated as well. All these nanostructures were obtained by VGS reaction of corresponding oxides with H2/H2S gases, at elevated temperatures (>800 °C), in a fluidized bed reactor (FBR) and a one-pot process. This success and apparent similarity between the two compounds "hid" from us the option of looking for the INT-MoS2 reaction parameters in entirely different regimes. The main challenge in the synthesis of INT-MoS2 via VGS was the instability of the in situ prepared suboxide nanowhiskers against over-reduction and recrystallization at high temperatures. The elucidated growth mechanism dictates separation of the reaction into five steps, as properties of the intermediate products are not consistent with a single process and require individual conditions for each step. A horizontal reactor with a porous-quartz reaction cell, which creates proper quasi-static (contrary to the FBR) conditions for the reaction involving sublimation, was imperative for the effective nanofabrication of INT-MoS2. These findings render a reproducible synthetic route for the production of highly crystalline pure-phase MoS2 nanotubes via a multistep VGS process, without the assistance of a catalyst and in a scalable fashion. Being a semiconductor, flexible, and strong, INT-MoS2 offers a platform for much research and numerous potential applications, particularly in the field of optoelectronics and reinforcement of polymer composites.

Low-temperature resonant Raman asymmetry in 2H-MoS2 under high pressure.

We report on the combined effect of temperature (6 K-300 K) and high pressure (up to 6 GPa) on the resonant Raman scattering by A1g phonons in bulk 2H-MoS2, as the energy of the A exciton is tuned into resonance with an exciting laser at EL = 1.96 eV. As expected, the pressure to be applied for attaining resonant conditions decreases with decreasing temperature. A striking result concerns the combined effect of temperature and pressure on the strength of the incoming relative to the outgoing resonance of the A1g phonon. When its Raman intensity is normalized by that of the 'non-resonant' [Formula: see text] phonon (IA1g/I[Formula: see text]), we find that the contribution of the pressure-tuned outgoing resonance relative to that of the incoming channel changes with temperature. At room temperature both contributions are about equal, as expected. Interestingly, with decreasing temperature an asymmetry in the relative magnitude of the resonances develops, becoming the outgoing contribution about half of the incoming resonance below ~50 K. We discuss the different possibilities for the origin of this effect.