Clarifying Glass Luminescence at Near-Infrared Excitation.

Glass is a unique material that is often encountered in chemical and biological studies as a convenient sample holder (vial or microscope slide in particular). If the sample is probed with light in fluorescence and Raman spectroscopic experiments, the contribution from glass is often present and can obscure the spectra from the analyte of interest. It is important to understand the nature of glass photoemission properties to control this potential interference. The Raman spectrum of glass is dominated by peaks around 500 and 1000 cm-1 at the excitation with UV and visible light. A strong broad emission band centered at 880 nm appears when glass is irradiated with near-infrared light, a popular 785 nm laser light in particular. We proved experimentally in this study that this broad band is due to glass photoluminescence and not Raman scattering. In addition, three narrow components were found to contribute to this band, which have different excitation profiles indicating that they originate from three different species or the same species experiencing three different types of local environments. It has been hypothesized that these peaks could be due to the presence of rare earth impurities in the glass. Further study is necessary to identify these luminescent centers.

Study of Oxidation and Polarization-Dependent Optical Properties of Environmentally Stable Layered GaTe Using a Novel Passivation Approach.

Emerging two-dimensional gallium chalcogenides, such as gallium telluride (GaTe), are considered promising layered semiconductors that can serve as vital building blocks towards the implementation of nanodevices in the fields of nanoelectronics, optoelectronics, and quantum photonics. However, oxidation-induced electronic, structural, and optical changes observed in ambient-exposed gallium chalcogenides need to be further investigated and addressed. Herein, we report on the thickness-dependent effect of air exposure on the Raman and photoluminescence (PL) properties of GaTe flakes, with thicknesses spanning in the range of a few layers to 100 nm. We have developed a novel chemical passivation that results in complete encapsulation of the as-exfoliated GaTe flakes in ultrathin hydrogen-silsesquioxane (HSQ) film. A combination of correlation and comparison of Raman and PL studies reveal that the HSQ-capped GaTe flakes are effectively protected from oxidation in air ambient over the studied-period of one year, and thus, preserving their structural and optical characteristics. This contrasts with the behavior of uncapped GaTe, where we observe a significant reduction of the GaTe-related PL (~100×) and Raman (~4×) peak intensities for the few-layered flakes over a period of few days. The time-evolution of the Raman spectra in uncapped GaTe is accompanied by the appearance of two new prominent broad peaks at ~130 cm-1 and ~146 cm-1, which are attributed to the formation of polycrystalline tellurium, due to oxidation of ambient-exposed GaTe. Furthermore, and by leveraging this novel passivation, we were able to explore the optical anisotropy of HSQ-capped GaTe flakes. This is caused by the one-dimensional-like nature of the GaTe layer, as the layer comprises Ga-Ga chains extending along the b-axis direction. In concurrence with high-resolution transmission electron microscopy analysis, polarization-dependent PL spectroscopy was used to identify the b-axis crystal direction in HSQ-capped GaTe flakes with various thicknesses over a range of wavelengths (458 nm-633 nm). Thus, our novel surface-passivation offers a new approach to explore and reveal the physical properties of the layered GaTe, with the potential of fabricating reliable polarization-dependent nanophotonics with structural and optical stability.

Core/shell nanofiber characterization by Raman scanning microscopy.

Core/shell nanofibers are becoming increasingly popular for applications in tissue engineering. Nanofibers alone provide surface topography and increased surface area that promote cellular attachment; however, core/shell nanofibers provide the versatility of incorporating two materials with different properties into one. Such synthetic materials can provide the mechanical and degradation properties required to make a construct that mimics in vivo tissue. Many variations of these fibers can be produced. The challenge lies in the ability to characterize and quantify these nanofibers post fabrication. We developed a non-invasive method for the composition characterization and quantification at the nanoscale level of fibers using Confocal Raman microscopy. The biodegradable/biocompatible nanofibers, Poly (glycerol-sebacate)/Poly (lactic-co-glycolic) (PGS/PLGA), were characterized as a part of a fiber scaffold to quickly and efficiently analyze the quality of the substrate used for tissue engineering.

Solid state and solution nitrate photochemistry: photochemical evolution of the solid state lattice.

We examined the deep UV 229 nm photochemistry of NaNO(3) in solution and in the solid state. In aqueous solution excitation within the deep UV NO(3)¯ strong π → π* transition causes the photochemical reaction NO(3)¯ → NO(2)¯ + O·. We used UV resonance Raman spectroscopy to examine the photon dose dependence of the NO(2)¯ band intensities and measure a photochemical quantum yield of 0.04 at pH 6.5. We also examined the response of solid NaNO(3) samples to 229 nm excitation and also observe formation of NO(2)¯. The quantum yield is much smaller at ∼10(-8). The solid state NaNO(3) photochemistry phenomena appear complex by showing a significant dependence on the UV excitation flux and dose. At low flux/dose conditions NO(2)¯ resonance Raman bands appear, accompanied by perturbed NO(3)¯ bands, indicating stress in the NaNO(3) lattice. Higher flux/dose conditions show less lattice perturbation but SEM shows surface eruptions that alleviate the stress induced by the photochemistry. Higher flux/dose measurements cause cratering and destruction of the NaNO(3) surface as the surface layers are converted to NO(2)¯. Modest laser excitation UV beams excavate surface layers in the solid NaNO(3) samples. At the lowest incident fluxes a pressure buildup competes with effusion to reach a steady state giving rise to perturbed NO(3)¯ bands. Increased fluxes result in pressures that cause the sample to erupt, relieving the pressure.

Deep ultraviolet resonance Raman excitation enables explosives detection.

We measured the 229 nm absolute ultraviolet (UV) Raman cross-sections of the explosives trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), cyclotrimethylene-trinitramine (RDX), the chemically related nitroamine explosive HMX, and ammonium nitrate in solution. The 229 nm Raman cross-sections are 1000-fold greater than those excited in the near-infrared and visible spectral regions. Deep UV resonance Raman spectroscopy enables detection of explosives at parts-per-billion (ppb) concentrations and may prove useful for stand-off spectroscopic detection of explosives.

Raman detected differential scanning calorimetry of polymorphic transformations in acetaminophen.

Acetaminophen is known to crystallize in three polymorphic forms. Thermally induced transformations between the crystalline forms and the super-cooled liquid have been observed by differential scanning calorimetry (DSC), but the assignment of calorimetric transitions to specific polymorphic transformations remains challenging, because the transition temperatures for several transformations are close to one another, and the characteristics of the observed transitions depend on experimental variables that are often poorly controlled. This paper demonstrates the simultaneous application of DSC and Raman microscopy for the observation of thermally driven transitions between polymorphs of pharmaceutical materials. Raman detected differential scanning calorimetry (RD-DSC) has been used to monitor the DSC thermograms of super-cooled liquid acetaminophen and confirms the assignment of two exothermic transitions to specific polymorphic transformations. Principal component analysis of the Raman spectra have been used to determine the number of independent components that participate in the phase transformations, and multivariate regression has been used to determine transition temperatures from the spectral data. The influence of the laser excitation source on measured DSC thermograms has also been investigated, and it has been demonstrated that a baseline shift occurs in RD-DSC when a polymorphic transformation occurs between crystalline and amorphous forms. RD-DSC has been used to examine the influence of sample aging and sample pan configuration on the observed polymorphic transformations, and both of these variables were found to influence the thermal behavior of the sample. The results demonstrate the advantage of simultaneous Raman spectroscopy and differential scanning calorimetry for the unambiguous assignment of thermally driven polymorphic transformations.