Paraelectric KH2_2PO4_4 Nanocrystals in Monolithic Mesoporous Silica: Structure and Lattice Dynamics

Combining dielectric crystals with mesoporous solids allows a versatile design of functional nanomaterials, where the porous host provides a mechanical rigid scaffold structure and the molecular filling adds the functionalization. Here, we report a study of the complex lattice dynamics of a SiO$_2$:KH$_2$PO$_4$ nanocomposite consisting of a monolithic, mesoporous silica glass host with KH$_2$PO$_4$ nanocrystals embedded in its tubular channels $\sim$12 nm across. A micro-Raman investigation performed in the spectral range of 70-1600 cm$^{-1}$ reveals the complex lattice dynamics of the confined crystals. Their Raman spectrum resembles the one taken from bulk KH$_2$PO$_4$ crystals and thus, along with X-ray diffraction experiments, corroborates the successful solution-based synthesis of KH$_2$PO$_4$ nanocrystals with a structure analogous to the bulk material. We succeeded in observing not only the high-frequency internal modes ($\sim$900-1200 cm$^{-1}$), typical of internal vibrations of the PO$_4$ tetrahedra, but, more importantly, also the lowest frequency modes typical of bulk KH$_2$PO$_4$ crystals. The experimental Raman spectrum was interpreted with a group theory analysis and first-principle lattice dynamics calculations. The analysis of calculated eigen-vectors indicates the involvement of hydrogen atoms in most phonon modes corroborating the substantial significance of the hydrogen subsystem in the lattice dynamics of paraelectric bulk and of KH$_2$PO$_4$ crystals in extreme spatial confinement. A marginal redistribution of relative Raman intensities of the confined compared to unconfined crystals presumably originates in slightly changed crystal fields and interatomic interactions, in particular for the parts of the nanocrystals in close proximity to the silica pore surfaces.Comment: 10 pages, 4 figures, in pres

Infrared Reflectance Analysis of Epitaxial n-Type Doped GaN Layers Grown on Sapphire

Abstract Infrared (IR) reflectance spectroscopy is applied to study Si-doped multilayer n+/n0/n+-GaN structure grown on GaN buffer with GaN-template/sapphire substrate. Analysis of the investigated structure by photo-etching, SEM, and SIMS methods showed the existence of the additional layer with the drastic difference in Si and O doping levels and located between the epitaxial GaN buffer and template. Simulation of the experimental reflectivity spectra was performed in a wide frequency range. It is shown that the modeling of IR reflectance spectrum using 2 × 2 transfer matrix method and including into analysis the additional layer make it possible to obtain the best fitting of the experimental spectrum, which follows in the evaluation of GaN layer thicknesses which are in good agreement with the SEM and SIMS data. Spectral dependence of plasmon-LO-phonon coupled modes for each GaN layer is obtained from the spectral dependence of dielectric of Si doping impurity, which is attributed to compensation effects by the acceptor states