Ge nanocrystals formed in a SiO 2 matrix by ion implantation were studied by Raman spectroscopy. It is shown that Raman analysis based on the phonon confinement model yields a successful explanation of the peculiar characteristics resulting from the nanocrystals. A broadening and a shift in the Raman peak are expected to result from the reduced size of the crystals. Asymmetry in the peak is attributed to the variations in the size of the nanocrystals. These effects were observed experimentally for the Ge nanocrystals prepared by ion implantation and explained theoretically by incorporating the effect of size and size distribution into the theoretical description of the Raman shift. A comparison with the transmission electron microscopy images indicated that this analysis could be used to estimate the structural properties of nanocrystals embedded in a host matrix. The evolution of nanocrystal formation with annealing temperature, i.e. the size growth, was monitored by Raman spectrometry for several samples and the corresponding nanocrystal sizes were estimated using the phonon confinement model.
Nanocrystalline Ge films were prepared by isotropic chemical etching on single-crystalline Ge substrates with 100 and 111 orientations. The structural and optical properties have been investigated by transmission electron microscopy (TEM), electron diffraction (ED), Raman photoluminescence (PL), and infrared spectroscopy. The average size of nanocrystals (NCs) was estimated by fitting of the Raman spectra using a phonon-confinement model developed for spherical semiconductor NCs. Considered collectively TEM, ED, and Raman results indicate that all films contain high density of 3–4 nm diameter, diamond-structured Ge NCs with disordered surfaces. There are indications that surface of nanoparticles is mainly hydrogen terminated even for air-stabilized samples. Red PL is observed at room temperature upon excitation by 1.96 eV with peak energy of ∼1.55 eV and correlates well with recent theoretical calculations of the enlarged optical gap in Ge NCs of similar size.
Electroluminescence (EL) and photoluminescence (PL) measurements were conducted on Si-implanted SiO 2 layers as a function of process and measurement parameters. Measurable light emission was observed from the metal oxide semiconductor light emitting diode (MOS-LED) when holes are injected from the substrate. It was shown that major PL and EL emissions have the same origin. However, two important differences were observed between EL and PL spectra. The first one is the light emission from the Si substrate due to the recombination of electrons supplied by the front contact and holes that were accumulated in the inversion region at the substrate/SiO 2 interface. This might be a factor reducing the contribution of Si nanocrystals to the EL emission of the MOS-LED structure as a result of decrease in the number of holes in the inversion layer. The second difference is that EL emission peaks stay at a slightly higher energy than PL peaks. It was observed that the EL peak shifts towards the PL peak with increasing bias voltage. This behaviour is explained by considering the size distribution of nanocrystals formed by ion implantation.
Nanocrystals embedded in SiO2 films are the subject of a number of recent works, mainly because of their potential usefulness in the fabrication of optoelectronic devices and nanocrystal memory structures. One interesting method for the fabrication of such nanocrystals is the ion implantation of segregating species into SiO2 films followed by heat treatment in order to induce nanocrystal formation. This method is both relatively simple and also compatible with the current MOS (metal-oxide-semiconductor) device technology. An unintentional effect can occur during the fabrication of nanocrystals using this method, namely a significant diffusion of the implanted species during annealing, away from the regions with the highest concentration. The Si∕SiO2 interface can be exposed to this diffusion flux. This can result in an altered interface and have a significant influence on electronic devices. Here, we report on ion implantation of Ge into SiO2 on Si followed by annealing under conditions, resulting in Ge accumulation at the Si∕SiO2 interface as determined by secondary-ion mass spectroscopy analysis, transmission electron microscopy with energy dispersive analysis of x-rays, and Rutherford backscattering spectrometry. The accumulation of Ge at the Si∕SiO2 interface has also been reported before. The resulting effect on the electronic structure of the interface is a priori unknown. We have fabricated MOS capacitors on the sample structures and their capacitance-voltage characteristics were measured and analyzed. We measure an interface state density around 1×1012cm−2, which is high compared to standard Si MOS devices. We discuss the results in terms of the previous electrical measurements on Ge-oxide interfaces and SiGe interfaces, which also can yield a high interface state density. The specific conditions we report result in a sufficiently low Ge concentration that nanocrystals are not segregated in the SiO2 film, while Ge still accumulates at the Si∕SiO2 interface after annealing.
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