Microstructure and optical properties of ZnO/porous silicon nanocomposite films

In this study, porous silicon (PS) templates were formed by electrochemical anodization on p-type (100) silicon wafer and ZnO films were deposited on PS substrates using radio frequency (RF) reactive magnetron sputtering technique. The effects of oxygen partial pressures of growth ZnO films and annealing ambience on the microstructure and photoluminescence (PL) of the ZnO/PS nanocomposite films were systematically investigated by X-ray diffraction and fluorescence spectrophotometry. The results indicated that all ZnO/PS nanocomposite films were polycrystalline in nature with a hexagonal wurtzite structure and the (002) oriented ZnO films had the best crystal quality under O₂:Ar ratio of 10:10 sccm and annealing in vacuum. PL measurements at room temperature revealed that ZnO/PS nanocomposite systems formed a broad PL band including the blue and green emissions from ZnO and red-orange emission from the PS. The mechanism and interpretation of broadband PL of the nanocomposites were discussed in detail using an oxygen-bonding model in PS and a native defects model in ZnO.     

Size dependence of the optical properties of silicon clusters

Ab initiocalculations of the optical properties of silicon clusters of 20, 60, and 70 atoms are presented. Quantum molecular dynamics using a minimal sp³basis set are performed to find metastable and equilibrium atomic configurations. The optical properties of these clusters are calculated using an extended sp³d⁵basis. We discuss the dependence of the optical properties on the number of atoms as well as on the geometric configuration of these clusters.     

Photoacoustic investigations of the optical absorption spectra of porous silicon layers on a silicon backing

This paper presents a series of experimental photoacoustic spectra of porous silicon layers on crystalline silicon and their numerical analysis performed in the proposed two-layer model. The goal of the analysis was to calculate the optical absorption spectra of porous silicon from the photoacoustic spectra of porous silicon layers on a silicon background. The experimental character of the observed absorption band associated with the porous silicon was revealed. This is the first attempt at a theoretical interpretation of the photoacoustic spectra of porous silicon on a silicon backing.     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

Birefringence and anisotropic optical absorption in porous silicon

The refractive indices and the coefficients of optical absorption by free charge carriers and local vibrations in porous silicon (por-Si) films, comprising nanometer-sized silicon residues (nanocrystals) separated by nanometer-sized pores (nanopores) formed in the course of electrochemical etching of the initial single crystal silicon, have been studied by polarization-resolved IR absorption spectroscopy techniques. It is shown that the birefringence observed in por-Si is related to the anisotropic shapes of nanocrystals and nanopores, while the anisotropy (dichroism) of absorption by the local vibrational modes is determined predominantly by the microrelief of the surface of nanocrystals. It is demonstrated that silicon-hydrogen surface bonds in nanocrystals can be restored by means of selective hydrogen thermodesorption with the formation of a considerable number of H-terminated surface Si-Si dimers.     

Inelastic light scattering and X-ray diffraction from thick free-standing porous silicon films

The results of Raman scattering and X-ray diffraction studies of thick, free-standing, porous Si layers with thickness up to 500 μm are presented. The Raman scattering spectra have a distinctive difference from previous data for porous Si films on Si substrate and for thin, free-standing, porous Si layers. The experimental data can be explained by a modified phonon confinement model that accounts for a comprehensive strained Si nanocrystal. The comprehensive strain is a tensile one, and the value of stress can be up to 3 GPa. This interpretation is supported by data of X-ray diffraction measurements.     

Ab initio absorption spectra and optical gaps in nanocrystalline silicon

The optical absorption spectra of Si(n)H(m) nanoclusters up to approximately 250 atoms are computed using a linear response theory within the time-dependent local density approximation (TDLDA). The TDLDA formalism allows the electronic screening and correlation effects, which determine exciton binding energies, to be naturally incorporated within an ab initio framework. We find the calculated excitation energies and optical absorption gaps to be in good agreement with experiment in the limit of both small and large clusters. The TDLDA absorption spectra exhibit substantial blueshifts with respect to the spectra obtained within the time-independent local density approximation.     

Size dependence of non-linear optical properties of SiO2 thin films containing InP nanocrystals

SiO₂ composite thin films containing InP nanocrystals were fabricated by radio-frequency magnetron co-sputtering technique. The microstructure of the composite thin films was characterized by X-ray diffraction and Raman spectrum. The optical absorption band edges exhibit marked blueshift with respect to bulk InP due to strong quantum confinement effect. Non-linear optical absorption and non-linear optical refraction were studied by a Z-scan technique using a single Gaussian beam of a He-Ne laser (632.8 nm). We observed the saturation absorption and two-photon absorption in the composite films. An enhanced third-order non-linear optical absorption coefficient and non-linear optical refractive index were achieved in the composite films. The nonlinear optical properties of the films display the dependence on InP nanocrystals size. Received: 27 June 2000 / Accepted: 27 June 2000 / Published online: 13 September 2000     

Growth and properties of PbTe films on porous silicon

The structural and electrical characteristics of vacuum deposited PbTe films on Si substrate with buffer porous silicon (PS) layer were investigated. Auger electron spectroscopy, electron and optical microscopy data have shown the absence of cracks, pores, metal and chalcogen microinclusions. A mosaic structure with a grain size of 20–60 μm was detected by selective chemical etching and acoustic microscopy methods. The investigations of X-ray diffraction and X-ray pole figures showed that grains have [100] orientation along the growth direction. The cooling–heating (300–77–300 K) cycles of multilayer PbTe/sublayer/Si structures did not lead to the processes of peeling or appearance of cracks. It was found that thick amorphous layers on a PS surface change the nature of PbTe films growth.     

Polarization phenomena in the optical properties of porous silicon

We examine the polarization memory effect for porous Si excited by linearly polarized light. The various observations for the red-luminescing, slow band are discussed in the general framework of particle shape asymmetry. We show that because of the intrinsically nonlinear luminescence response, measurement parameters influence the polarization response. The preparation of porous Si with photoassisted etching is found to control the polarization retention parameter ρ. Using linearly polarized light during etching produces in-plane asymmetries. We find a substantial ρ-anisotropy linked to crystal symmetry planes and axes as a consequence of anisotropic etching. The effects are discussed with reference to current models of the light emission mechanism.     

Self detachment of free-standing porous silicon membranes in moderately doped n-type silicon

In this article we describe a reliable etching method to fabricate porous silicon free-standing membranes (FSMs) based on a self detachment of the porous layer in moderately doped n-type silicon substrates. We found that stable growth of smooth and straight pores is restricted to a narrow range of etching conditions and, unlike p-type substrates, the lift-off of the membrane is a self-limited process that does not require a large burst of current. The detachment of the porous membrane is independent of the structure of the already porosified layer, meaning that the average pore diameter can be tuned from nano to macro size within the same membrane. We also demonstrate that, despite their limited thickness, FSMs are quite robust and can sustained further processing. Thus, the etching receipt we are proposing here extends the range of sensors and filters that can be fabricated using porous silicon technology.     

Temperature dependence of anomalous structure in the derivative absorption spectra of Si:P

Temperature dependence of wavelength-derivative absorption spectra of Si:P has been measured, with emphasis on temperature behaviors of anomalous exciton-absorption structure previously observed nearly at the free-exciton absorption thresholds. Such anomalous structure has been observed even at high temperatures where the principal bound-exciton component almost disappears. This result confirms our previous identification that the structure is related to free-exciton absorption rather than bound-exciton absorption.     

Peculiarities of the reflection spectra of PECVD nanocrystalline porous silicon films

Photoluminescent nanocrystalline porous silicon films have been formed on silicon substrates by plasma-enhanced chemical vapor deposition. In the visible spectral range, a nontrivial character of the reflection spectra (dependent on the film thickness) has been found. The sizes of crystallites and the root-mean-square roughness of the deposited film surface have been determined by X-ray diffraction and atomic force microscopy. It is shown that the significant decrease in the reflectance in the spectral range from 200 to 900 nm and the red shift of the characteristic peaks in the reflection spectra are related to the sizes of nanocrystallites in the films formed.     

Size effect in optical spectra of microcrystalline diamond powders and CVD films

Received: 24 March 1997/Accepted: 27 May 1997     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Anomalous birefringence of light in free-standing samples of porous silicon

The birefringence of light in freely suspended samples of porous silicon is observed and investigated. The effect is interpreted as “shape birefringence,” i.e., the effect caused by the structure of a material consisting of anisotropic formations with sizes less than the wavelength of the light and with a predominant orientation. It is checked experimentally that the samples do not possess optical activity or optical anisotropy in the plane of the porous-silicon film. It is determined that the effect is observed for polarization of incident light that rules out the possibility of observing birefringence in a uniform optical medium, and it is not observed in the conventional experimental geometry. Qualitative explanations are given for the anomalous character of the observed defect.