We report a detailed study of the strong near-field Raman scattering enhancement which takes place in tipenhanced Raman scattering (TERS) in indium nitride. In addition to the well-known first-order optical phonons of indium nitride, near-field Raman modes, not detectable in the far-field, appear when approaching the plasmonic probe. The frequencies of these modes coincide with calculated energies of second order combinational modes consisting of optical zone center phonons and acoustic phonons at the edge of the Brillouin zone. The appearance of strong combinational modes suggests that TERS in indium nitride represents a special case of Raman scattering in which a resonance condition on the nanometer scale is achieved between the localized surface plasmons (LSPs) and surface plasmon polaritons (SPPs) of the probe with the surface charge oscillation of the material. We suggest that the surface charge accumulation (SCA) in InN, which can render the surface a degenerate semiconductor, is the dominating reason for the unusually large enhancement of the TERS signal as compared to other inorganic semiconductors. Thus, the plasmon-resonant TERS (PR-TERS) process in InN makes this technique an excellent tool for defect characterization of indium-rich semiconductor heterostructures and nanostructures with high carrier concentrations.
Ternary semiconductors such as InGaN thin films, quantum wells, and superlattices commonly exhibit alloy fluctuations that become increasingly pronounced with higher In-content. The thickness fluctuations of quantum wells and their thin cap-layers further introduce nanoscale inhomogeneities that alter the potential landscape. In this work, we present a combined theoretical and experimental study of InGaN single quantum wells with thin GaN cap-layers to unravel the influence of cap-layer thickness, compositional inhomogeneity, and thickness fluctuations on their electronic and optical properties. A pronounced spectral shift of quantum well emission for thin cap-layers between 1 and 10 nm is observed by micro-photoluminescence spectroscopy. The origin of this shift is explained by calculations of electronic band profiles and probability density overlap of carriers in the quantum well. The impact of alloy fluctuations and homogeneity for different cap-layer thicknesses is studied on both the microscale and nanoscale using UV micro-Raman scattering and tip-enhanced Raman spectroscopy (TERS). On the microscale, the alloy composition as determined by micro-Raman mapping appears very homogeneous except for the thinnest 1 nm cap-layer where small fluctuations are visible. On the nanoscale, TERS reveals local fluctuations on a 20–30 nm length scale. The influence of the cap-layer thickness on the TERS spectra is discussed regarding both the nanoscale homogeneity and the depth resolution of the near-field Raman scattering technique. Our results demonstrate the capabilities of TERS to resolve nanoscale thickness fluctuations and compositional inhomogeneities in ultra-thin semiconductor layers, even when they are buried by thin cap-layers with thicknesses below 10 nm.
The luminescence of InxGa1-xN nanowires (NWs) is frequently reported with large red-shifts as compared to the theoretical value expected from the average In-content. Both, compositional fluctuations and radial built-in fields...
Continuous manufacturing is becoming the new technological standard in the pharmaceutical industry. In this work, a twin-screw processor was employed for the continuous production of liquisolid tablets containing either simethicone or a combination of simethicone with loperamide hydrochloride. Both active ingredients present major technological challenges, as simethicone is a liquid, oily substance, and loperamide hydrochloride was used in a very small amount (0.27% w/w). Despite these difficulties, the use of porous tribasic calcium phosphate as a carrier and the adjustment of the settings of the twin-screw processor enabled the optimization of the characteristics of the liquid-loaded powders and made it possible to efficiently produce liquisolid tablets with advantages in physical and functional properties. The application of chemical imaging by means of Raman spectroscopy allowed for the visualization of differences in the distribution of individual components of the formulations. This proved to be a very effective tool for identifying the optimum technology to produce a drug product.
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