Ge nanocrystals embedded in thermal SiO2 on top of a Si substrate are investigated using Raman spectroscopy and transmission electron microscopy. We observe that the Raman peak frequency of the Ge nanocrystals is strongly affected by compressive stress. In the case of large particles for which the phonon confinement-induced Raman shift can be neglected, the stress is measured taking into account isotopic composition effects induced by the ion implantation process used to produce the nanocrystals. The stress is proposed to originate from a liquid–solid phase transition in Ge.
Porous silicon thin films created under laser illumination in fluoride solutions without biasing have been studied by a variety of techniques to investigate the film structure and photoluminescence (PL). The use of ultrathin silicon wafers allows us to perform plan view transmission electron microscopy studies without recourse to thinning procedures that might adversely affect the film structure. Supercritically dried samples are compared to air dried samples and clearly demonstrate the deleterious effects of air drying on film structure. PL studies were performed (a) while the sample is submerged in aqueous HF, (b) in Ar after rinsing in ethanol, and (c) in air after rinsing in ethanol. The wavelength of light used to fabricate the film is found to correlate strongly with the peak PL wavelength when measured in solution. Little correlation is found in Ar or in air. Exposure to air can change the PL spectrum dramatically on a time scale of just seconds. We demonstrate that samples can exhibit essentially identical PL spectra in one medium but have spectra that differ from one another when the samples are placed in a different medium. The PL results indicate that band-to-band recombination cannot explain photon emission under all circumstances, and that surface states must also be involved in radiative processes under those conditions in which the bands are sufficiently separated to allow for the appearance of gap states.
Calculations of the electron-acoustic phonon interaction, and Raman scattering efficiency, in matrix embedded Ge quantum dots ͑QDs͒ are presented. The work is focused on the understanding of the inelastic light scattering process excited close to resonance with the confined E 1 transitions. Due to the large joint density of states at the E 1 point, many intermediate electronic states contribute to the overall scattering efficiency. This particular situation leads to quantum interference effects between different scattering paths and has, therefore, a strong impact on the Raman line shapes and intensities. Quantum confinement of the electron and hole states is treated within the envelope wave function approximation. The QD/matrix acoustic vibrations are deduced from elasticity theory. Deformation-potential interaction between the electrons ͑and holes͒ and acoustic vibrations is assumed. The resonant Raman spectra are calculated using third order perturbation quantum theory. A Raman-Brillouin electronic density is constructed as a linear combination of the electronic states involved in the inelastic light scattering. It allows one to plot, for each excitation energy, the spatial distribution of the electronic density that gives rise to the Raman ͑or Brillouin͒ signal. It is calculated for both diagonal and off-diagonal transitions between the confined electronic states. The dependence of the spectral line shapes and intensities on homogeneous broadening of the E 1 transitions, QD size, surface boundary conditions is discussed in details. The calculated spectra are then compared to those measured for different QD size distributions.
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