Effects of thermal oxidation on the photoluminescence properties of porous silicon

The effects of thermal oxidation on the photoluminescence (PL) properties of powdered porous silicon (PSi) are studied using X-ray photoelectron spectroscopy (XPS). It is found that the PL intensity is steeply quenched after annealing at and recovered at above . The XPS intensity of oxides formed on the PSi surface is also found to strongly depend on the annealing temperature. The comparison between the annealing temperature dependence of PL intensity and that of the oxide XPS intensity suggests that the formation of thin disordered SiO₂ layer accompanies the quenching of the PL intensity, and that the formation of thick high-quality SiO₂ layer results in the PL intensity recovery. These results indicate that the thickness and quality of SiO₂ layer play a crucial role in the PL properties of thermally oxidized PSi.     

All porous silicon microcavities: growth and physics

The spontaneous emission of a material can be controlled by placing it in a micron-sized optical cavity. In this paper we introduce the subject and we discuss the realization, the physics and perspective applications of all porous silicon microcavities. The emission properties of the cavities have been characterized as a function of the temperature, of the excitation power and of the response time. Coupled microcavities are demonstrated. Modeling of the structure have been performed on the basis of a transfer matrix approximation.     

The room temperature oxidation of porous silicon

The room temperature oxidation of porous silicon was studied using isothermal methods. The oxidation was found to depend on the type of the porous silicon. The microcalorimetric signals from the oxidation of the p⁺- and n-type porous silicon in dry air were different. In humid air the signals from the oxidation could not be distinguished from the strong signal due to adsorption of water vapour, but when the samples were placed in water similar differences were observed. The reason for differences in reactions is discussed. The oxidation in different liquids was also studied. The signal from reactions in methanol and ethanol were found to be 100 times higher than in water. In FTIR studies the reaction gas produced by reactions between alcohols and the porous silicon, silane (SiH₄) was found in the gas. Traces of SiOCH₃ and SiOC₂H₅ groups were also found in FTIR spectra indicating Si---O---C_xH_y passivation of the surface.     

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.     

Ellipsometric study of refractive index anisotropy in porous silicon

Porous Si layers of different thicknesses were prepared by anodising p⁺-type Si substrates with a resistivity of 0.01 Ω cm. The porosity of the samples ranged from 23% to 62%. The refractive index values for the ordinary and extraordinary rays were determined by multiple angle of incidence ellipsometry, from which an optical anisotropy parameter varying from 13% to 20% was obtained. The porous Si layers were modelled as uniaxially anisotropic films on an isotropic substrate, with an optical axis perpendicular to the sample surface. The morphological anisotropy which is typical for the p⁺-type porous Si with a predominating cylindrical geometry is responsible for these optical properties. All the porous Si layers studied were found to be optically negative.     

Interference filters from porous silicon with laterally varying wavelength of reflection

Porous silicon reflection interference filters of Bragg type consists of up to 40 quarter wave layers with alternating high- and low-refraction index. The refraction index depends on the porosity of the silicon. The reflection wavelength can vary over a wide range and depends on the thickness and refraction index of the porous layers. A laterally continuously varying wavelength with linear profile of the filter can be achieved by manipulating the porosity and thickness of the silicon in the lateral direction. Our approach is to vary the Fermi level laterally by applying a potential parallel to the surface of the wafer. The slope of the Fermi level is easily controlled by the magnitude of the potential. The lateral current density and thus the porosity and thickness is related to the potential difference between the laterally varying Fermi level and the potential induced by the counter electrode. This relation is the well-known current–voltage characteristic of a Silicon hydrofluoric acid contact. The linearity of the etch profile across the wafer is demonstrated and the properties of preliminary reflection filters are shown.     

Confinement in a planar waveguide with porous silicon omnidirectional mirrors as confining walls

We present the design and study of waveguide structures based on porous silicon where the light confinement is not due to the usual total reflection effect but to the use of photonic crystals (PCs) as confining walls. These PC are omnidirectional mirrors (OMs), consisting of the periodic repetition of two porous silicon layers with different refractive indices and thicknesses. They reflect the radiation for all angles of incidence within a frequency range called the omnidirectional band gap (OBG). We have followed the PC formalism to investigate the properties of the OM as a multimode waveguide: the number of modes within the band gap, their field spatial distribution and their confinement as a function of the frequency and the core thickness.     

Solvent detection using porous silicon optical waveguides

Since the first report on the use of porous silicon as an optical waveguide medium in 1995, significant development has been made towards the understanding and applicability of such material. Here, the introduction of solvents (acetone, methanol, and propan-2-ol) into the pores is shown to dramatically reduce the loss of the waveguides, in a reversible manner. Both the magnitude and duration of this effect are sensitive to the solvent introduced. In some waveguides, for example, the measured loss (at 0.633 μm) falls by as much as 34 dB cm⁻¹ on the introduction of acetone. Theoretical estimates of the effect of solvents on the interfacial scattering loss confirm this as the origin of the observed reductions. These results, combined with the fact that a substantial portion of the guided-mode field interacts with the solvent, indicate an enhanced sensitivity for sensor applications may be achievable.     

Irreversible quenching of luminescence in porous silicon

The influence of applied voltage on photoluminescence (PL) in porous silicon was studied. A strong PL band around 680 nm was observed when excited by a 300 nm ultraviolet light with no voltage applied, but upon increasing the bias voltage, a strong and progressive decrease of the PL intensity was observed leading finally to a complete quenching of the emitted light at 1.80 V. The peak position of the emission appears to be stable. This effect is completely irreversible, and the spectra depend on the increased voltage to the sample and corresponding temperature increase. Nonradiative recombination resulting from the thermal oxidation was suggested to be responsible for the quenching.     

Study of porous silicon optical waveguides impregnated with organic dyes

Planar waveguides were made using oxidised porous silicon layers. Then, they were impregnated with Congo Red or Disperse Red 1 dyes. Optical losses were investigated before and after impregnation. In our case, the losses of impregnated waveguides were always higher than those of non-impregnated ones. In order to achieve a better understanding of the origin of these losses, we not only studied the absorbance of solutions which would impregnate the porous layers but also the reflectance spectra of the obtained composite materials. According to the measurements, the increase in losses in the visible spectrum depends on the intrinsic absorption of the dye while in NIR, the increase would be due to an accumulation of dried dye on the surface of the waveguide which would give rise to the surface scattering losses.     

The role of surface oxidation on luminescence degradation of porous silicon

This study reports a comparative analysis on time dependent degradation of photoluminescence (PL) spectra of porous silicon (PS) during dark-aging (DA) and photo-aging (PA). Fourier Transform Infrared (FTIR) spectroscopy studies have been performed to get an insight on possible chemical changes in the PS surface. It has been found that SiH_x bonds decrease progressively while SiO_x bonds increase. FTIR and PL measurements revealed presence of blue shifts in the PL spectra during the aging stages (PA and DA). While the PL intensity of dark aged PS shows a decrease during the first 3 weeks and an increase afterwards, the PL intensity decreases continuously for photo-aged PS. The change in the PL spectra has been investigated by overlapping of two different PL bands which are reflective of oxidation of PS surface and size of Si naonocrystallites. A possible bond configuration model about the oxidation of PS surface has also been proposed. The results are interpreted in terms of quantum size effects in PS and the influence of the surface composition.     

Efficient luminescence from porous silicon

Photoluminescence measurements are carried out on porous silicon layers. We show the enhancement and stabilization of the luminescence when depositing a silicon nitride layer on top of porous layers.We also demonstrate that direct- and remote-plasma nitridation are good ways to reduce the ageing effect of porous silicon layers due to a passivation of dangling bonds.     

Optical waveguides in porous silicon pre-patterned by localised nitrogen implantation.

FIPOS technology forms islands of silicon isolated from a silicon substrate by (oxidised) porous silicon. The larger refractive index of the silicon islands suggests their use as optical waveguides. Sets of these silicon islands have been fabricated and the anticipated waveguiding has been observed at wavelengths of 1.15 and 1.3 μm in the silicon islands. However, the dominant waveguiding in these FIPOS structures is observed in the porous silicon between the silicon islands, close to the sample surface. A simple dynamic model of the anodisation process has been developed to explain the origin of this unexpected waveguiding.     

Controlling surface states and photoluminescence of porous silicon by low-energy-ion irradiation

Porous silicon (PS) was irradiated by three kinds of low-energy ions with different chemical activity, namely argon ions, nitrogen ions and oxygen ions. The chemical activity of ions has significant effect on the surface states and photoluminescence (PL) properties of PS, The photoluminescence quenching after argon ions and nitrogen ions irradiation is ascribed to the broken Si-Si bonds, while the PL recovery is attributed to the oxidation of Si-H back bonds. Oxygen ions irradiation leads to the formation of a SiO_x layer with oxygen defects and PS shows different PL evolution than PS irradiated by argon ions and nitrogen ions.     

Light emission from porous silicon single and multiple cavities

Experimental and theoretical techniques are used to examine the effects of microstructuring on the optical properties of multilayer, single and multiple microcavity structures fabricated from porous silicon. Measurements of the reflectivity and photoluminescence spectra of three multilayer samples are presented. The results are modelled using a transfer matrix technique including a negative absorption term to represent the effect of spontaneous emission which gives luminescence. The emitted light is strongly controlled by the optical modes of the structures and very good agreement is observed between theory and experiment.     

Photoluminescence and electroluminescence from porous silicon

The properties and origins of the red, blue and infrared photoluminescence bands of porous silicon are reviewed and discussed in the light of the models that have been proposed to explain the experimental and theoretical results. The red band is due to quantum confinement possibly supplemented by surface states; the blue band is linked to the presence of silicon dioxide; the infrared band is correlated with dangling bonds and bandgap luminescence in large crystallites. The fabrication and characterization of light-emitting devices made of porous silicon are reported and discussed with respect to critical issues such as the device stability, efficiency, modulation speed, emission wavelength, and compatibility with microelectronic processing.     

Low-porosity porous silicon nanostructures on monocrystalline silicon solar cells

In this work we present a study of low-porosity porous silicon (PS) nanostructures stain etched on monocrystalline silicon solar cells. The PS layers reduce the reflectance, improve the diffusion of dopants by rapid thermal processes, and increase the homogeneity of the sheet resistance. Some samples were subjected to chemical oxidation in HNO₃ to reduce the porosity of the surface layer. After the diffusion process, deposition of a SiN_x antireflection layer, and screen printing of the samples, an efficiency of 15.5% is obtained for low-porosity PS solar cells, compared with an efficiency of 10.0% for standard PS cells and 14.9% for the reference Cz cells.     

Optical properties of erbium-doped porous silicon waveguides

Planar and buried channel porous silicon waveguides (WG) were prepared from p⁺-type silicon substrate by a two-step anodization process. Erbium ions were incorporated into pores of the porous silicon layers by an electrochemical method using ErCl₃-saturated solution. Erbium concentration of around 10²⁰ at/cm³ was determined by energy-dispersive X-ray analysis performed on SEM cross-section. The luminescence properties of erbium ions in the IR range were determined and a luminescence time decay of 420 μs was measured. Optical losses were studied on these WG. The increased losses after doping were discussed.     

Influence of experimental parameters on physical properties of porous silicon and oxidized porous silicon layers

This paper reports physical properties of porous silicon and oxidized porous silicon, manufactured by anodisation from heavily p-type doped silicon wafers as a function of experimental parameters. The growth rate and refractive index of the layers were studied at different applied current densities and glycerol concentrations in electrolyte. When the current density varied from 5 to 100 mA/cm², the refractive index was between 1.2 and 2.4 which corresponded to a porosity range from 42 to 85%. After oxidation, the porosity decreased and was between 2 and 45% for a refractive index range from 1.22 to 1.46. The thermal processing also induced an increase in thickness which was dependent on the initial porosity. This increase in thickness was more important for the lowest porosities. Lastly, the roughness of the porous layer/silicon substrate interface was studied at different applied current densities and glycerol concentrations in solution. Roughness decreased when the current density or glycerol concentration increased. Moreover, roughness was also reduced by thermal oxidation.     

Improvement of photoluminescence properties of porous silicon by silica passivation

Porous silicon (PS) was passivated by silica film using a sol-gel method; the photoluminescence (PL) properties were significantly improved; namely, PL intensity and stability increased and PL peak shifted to shorter wavelength. Scanning electron microscope (SEM) and Fourier transformed infrared spectroscope (FTIR) results indicated that silica passivation produced a compact film on the PS surface and modified the surface state of PS. The number of stable surface bonds (HSiO₃, HSiSiO₂ and H₂SiO₂) increased due to the oxidation of SiH back-bonds during the gelation process, and thus the PL intensity and stability were improved. Moreover, the blue-shift of PL peak was determined due to the increase in the ratio of SiO/SiH.