Quantum confinement (QC) typically assumes a sharp interface between a nanostructure and its environment, leading to an abrupt change in the potential for confined electrons and holes. When the interface is not ideally sharp and clean, significant deviations from the QC rule appear and other parameters beyond the nanostructure size play a considerable role. In this work we elucidate the role of the interface on QC in Ge quantum dots (QDs) synthesized by rf-magnetron sputtering or plasma enhanced chemical vapor deposition (PECVD). Through a detailed electron energy loss spectroscopy (EELS) analysis we investigated the structural and chemical properties of QD interfaces. PECVD QDs exhibit a sharper interface compared to sputter ones, which also evidences a larger contribution of mixed Ge-oxide states. Such a difference strongly modifies the QC strength, as experimentally verified by light absorption spectroscopy. A large size-tuning of the optical bandgap and an increase in the oscillator strength occur when the interface is sharp. A spatially dependent effective mass (SPDEM) model is employed to account for the interface difference between Ge QDs, pointing out a larger reduction in the exciton effective mass in the sharper interface case. These results add new insights into the role of interfaces on confined systems, and open the route for reliable exploitation of QC effects.
Determination of the optical bandgap (Eg) in semiconductor nanostructures is a key issue in understanding the extent of quantum confinement effects (QCE) on electronic properties and it usually involves some analytical approximation in experimental data reduction and modeling of the light absorption processes. Here, we compare some of the analytical procedures frequently used to evaluate the optical bandgap from reflectance (R) and transmittance (T) spectra. Ge quantum wells and quantum dots embedded in SiO2 were produced by plasma enhanced chemical vapor deposition, and light absorption was characterized by UV-Vis/NIR spectrophotometry. R&T elaboration to extract the absorption spectra was conducted by two approximated methods (single or double pass approximation, single pass analysis, and double pass analysis, respectively) followed by Eg evaluation through linear fit of Tauc or Cody plots. Direct fitting of R&T spectra through a Tauc-Lorentz oscillator model is used as comparison. Methods and data are discussed also in terms of the light absorption process in the presence of QCE. The reported data show that, despite the approximation, the DPA approach joined with Tauc plot gives reliable results, with clear advantages in terms of computational efforts and understanding of QCE.
Germanium quantum dots (QDs) embedded in SiO2 or in Si3N4 have been studied for light harvesting purposes. SiGeO or SiGeN thin films, produced by plasma enhanced chemical vapor deposition, have been annealed up to 850 °C to induce Ge QD precipitation in Si based matrices. By varying the Ge content, the QD diameter can be tuned in the 3–9 nm range in the SiO2 matrix, or in the 1–2 nm range in the Si3N4 matrix, as measured by transmission electron microscopy. Thus, Si3N4 matrix hosts Ge QDs at higher density and more closely spaced than SiO2 matrix. Raman spectroscopy revealed a higher threshold for amorphous-to-crystalline transition for Ge QDs embedded in Si3N4 matrix in comparison with those in the SiO2 host. Light absorption by Ge QDs is shown to be more effective in Si3N4 matrix, due to the optical bandgap (0.9–1.6 eV) being lower than in SiO2 matrix (1.2–2.2 eV). Significant photoresponse with a large measured internal quantum efficiency has been observed for Ge QDs in Si3N4 matrix when they are used as a sensitive layer in a photodetector device. These data will be presented and discussed, opening new routes for application of Ge QDs in light harvesting devices.
One of the most promising approaches to produce industrial compatible Transparent Conducting Materials (TCMs) with excellent characteristics is the fabrication of TCO/metal/TCO multilayers. In this article, we report on the electro-optical properties of a novel high-performing TCO/metal/TCO structure in which the intra-layer is a micro-structured metallic grid instead of a continuous thin film. The grid is obtained by evaporation of Ag through a mask of polystyrene colloidal micro-spheres deposited by the Langmuir-Blodgett method and partially dry-etched in plasma. IZO/Ag grid/IZO structures with different thicknesses and mesh dimensions have been fabricated, exhibiting excellent electrical characteristics (sheet resistance below 10 Ω/□) and particularly high optical transmittance in the near-infrared spectral region as compared to planar (unstructured) TCM multilayers. Numerical simulations were also used to highlight the role of the Ag mesh parameters on the electrical properties.
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