Localization of acoustic modes in periodic porous silicon structures

The propagation of longitudinal acoustic waves in multilayer structures based on porous silicon and the experimental measurement of acoustic transmission for the structures in the gigahertz range are reported and studied theoretically. The considered structures exhibit band gaps in the transmission spectrum and these are localized modes inside the band gap, coming from defect layers introduced in periodic systems. The frequency at which the acoustic resonances appear can be tuned by changing the porosity and/or thickness of the defect layer.     

Tunable resonance transmission modes in hybrid heterostructures based on porous silicon

ABSTRACT: In this work, we report the experimental results and theoretical analysis of strong localization of resonance transmission modes generated by hybrid periodic/quasiperiodic heterostructures (HHs) based on Porous Silicon (PSi). The HHs are formed by stacking a quasiperiodic Fibonacci (FN) substructure between two Distributed Bragg Reflectors (DBRs). FN substructure defines the number of strong localized modes that can be tunable at any given wavelength and be unfolded when a partial periodicity condition is imposed. These structures show interesting properties for biomaterials research, biosensor applications and basic studies of adsorption of organic molecules. We also demonstrate the sensitivity of HHs to material infiltration.     

Diffusion in porous silicon: effects on the reactivity of alkenes and electrochemistry of alkylated porous silicon

Alkenes are known to react with hydrogen-terminated silicon surfaces to produce robust organic monolayers that are attached to the surface via covalent SiC bonds. In this report we investigate the dependence of the rate of alkylation of porous silicon samples on the reaction time using photochemical initiation. The kinetics of the photochemical alkylation of hydrogen-terminated porous silicon by undec-1-ene in toluene were observed to be pseudo first order, however the apparent rate constant decreased as the concentration of undec-1-ene increased. This behaviour is opposite to what would be expected if the rate-limiting process was an elementary chemical reaction step involving the alkene. Instead, it suggests that transport of the alkene to reactive sites and in the correct orientation is the rate-limiting step. Comparison of the rates of alkylation of porous silicon by undec-1-ene and dimethoxytrityl (DMT)-undecenol is consistent with such an interpretation as the bulky DMT headgroup gives a lower rate of alkylation. The diffusion of some simple redox-active probe molecules in porous silicon was investigated using a scanning electrochemical microscope (SECM). The probe molecules are converted at diffusion-controlled rate at an inlaid disk ultramicroelectrode (UME) consisting of the cross-section of a microwire sealed in glass. If the microelectrode is placed a short distance above the porous silicon, the microelectrode current depends on kinetics of the electrochemical reactions at the porous silicon and the mass transport properties within the open thin layer cell formed by the microelectrode and the alkylated porous silicon. In order to differentiate the effects of finite heterogeneous kinetics at silicon from diffusion limitations, current-distance curves were fitted over a wide range of applied potentials (on the Si) and it was observed that the diffusion coefficient in the porous layer was strongly anisotropic. The measured diffusion rates are comparable to those in bulk water along the pores, but with negligible diffusion between pores. This indicates that few pore-pore interconnections exist in the porous silicon.     

Monitoring of degradation of porous silicon photonic crystals using digital photography

We report the monitoring of porous silicon (pSi) degradation in aqueous solutions using a consumer-grade digital camera. To facilitate optical monitoring, the pSi samples were prepared as one-dimensional photonic crystals (rugate filters) by electrochemical etching of highly doped p-type Si wafers using a periodic etch waveform. Two pSi formulations, representing chemistries relevant for self-reporting drug delivery applications, were tested: freshly etched pSi (fpSi) and fpSi coated with the biodegradable polymer chitosan (pSi-ch). Accelerated degradation of the samples in an ethanol-containing pH 10 aqueous basic buffer was monitored in situ by digital imaging with a consumer-grade digital camera with simultaneous optical reflectance spectrophotometric point measurements. As the nanostructured porous silicon matrix dissolved, a hypsochromic shift in the wavelength of the rugate reflectance peak resulted in visible color changes from red to green. While the H coordinate in the hue, saturation, and value (HSV) color space calculated using the as-acquired photographs was a good monitor of degradation at short times (t < 100 min), it was not a useful monitor of sample degradation at longer times since it was influenced by reflections of the broad spectral output of the lamp as well as from the narrow rugate reflectance band. A monotonic relationship was observed between the wavelength of the rugate reflectance peak and an H parameter value calculated from the average red-green-blue (RGB) values of each image by first independently normalizing each channel (R, G, and B) using their maximum and minimum value over the time course of the degradation process. Spectrophotometric measurements and digital image analysis using this H parameter gave consistent relative stabilities of the samples as fpSi > pSi-ch.     

Detection of nerve agent stimulants based on photoluminescent porous silicon interferometer

Porous silicon (PSi) exhibiting dual optical properties, both Fabry-Pérot fringe and photolumincence, was developed and used as chemical sensors. PSi samples were prepared by an electrochemical etch of p-type silicon under the illumination of 300-W tungsten lamp during the etch process. The surface of PSi was characterized by cold field-emission scanning electron microscope. PSi samples exhibited a strong visible orange photoluminescence at 610 nm with an excitation wavelength of 460 nm as well as Fabry-Pérot fringe with a tungsten light source. Both reflectivity and photoluminescence were simultaneously measured under the exposure of organophosphate vapors. An increase of optical thickness and quenching photoluminescences under the exposure of various organophosphate vapors were observed.     

Transient surface photovoltage studies of bare and Ni-filled porous silicon performed in different ambients

Mesoporous silicon and porous silicon/Ni nanocomposites have been investigated in this work employing light-dark surface photovoltage (SPV) transients to monitor the response of surface charge dynamics to illumination changes. The samples were prepared by anodization of a highly n-doped silicon wafer and a subsequent electrodepositing of Ni into the pores. The resulting pores were oriented towards the surface with an average pore diameter of 60 nm and the thickness of the porous layer of approximately 40 μm. SPV was performed on a bare porous silicon as well as on a Ni-filled porous silicon in vacuum and in different gaseous environments (O₂, N₂, Ar). A significant difference was observed between the ‘light-on’ and ‘light-off’ SPV transients obtained in vacuum and those observed in gaseous ambiences. Such behavior could be explained by the contribution to the charge exchange in gas environments from chemisorbed and physisorbed species at the semiconductor surface.

PACS

81.05.Rm; 73.20.-r; 75.50.-y; 82.45.Yz     

Study of the omnidirectional photonic band gap for dielectric mirrors based on porous silicon : effect of optical and physical thickness

ABSTRACT: We report the theoretical comparison of the omnidirectional photonic band gap (OPBG) of one-dimensional dielectric photonic structures, using three different refractive index profiles: sinusoidal, Gaussian and Bragg. For different values of physical thickness (PT) and optical thickness (OT), the tunability of the OPBG of each profile is shown to depend on the maximum/minimum refractive indices. With an increase in the value of the maximum refractive index, the structures with the same PT, showed a linear increment of the OPBG; in contrast to the structures with the same OT, showing an optimal combination of refractive indices for each structure to generate the maximum OPBG. An experimental verification was carried out with a multilayered dielectric porous silicon structure for all the three profiles.     

Morphological and nanostructural features of porous silicon prepared by electrochemical etching

Porous layers were produced on a p-type (100) Si wafer by electrochemical anodic etching. The morphological, nanostructural and optical features of the porous Si were investigated as functions of the etching conditions. As the wafer resistivity was increased from 0.005 to 15 Ω·cm, the etched region exhibited ‘sponge’, ‘mountain’ and ‘column’-type morphologies. Among them, the sponge-type structured sample showed the largest surface area per unit volume. Silicon nanocrystallites, 2.0 to 5.3 nm in size, were confirmed in the porous layers. The photoluminescence peaks varied in the wavelength range of 615 to 722 nm. These changes in the maximum peak position were related to the size distribution of the Si crystallites in the porous silicon. The doping levels of the wafers significantly affect the size distribution of the Si crystallites as well as the light-emitting behavior of the etched Si, which contains nanoscale Si crystallites.     

Comparative study of initial stages of copper immersion deposition on bulk and porous silicon

Initial stages of Cu immersion deposition in the presence of hydrofluoric acid on bulk and porous silicon were studied. Cu was found to deposit both on bulk and porous silicon as a layer of nanoparticles which grew according to the Volmer-Weber mechanism. It was revealed that at the initial stages of immersion deposition, Cu nanoparticles consisted of crystals with a maximum size of 10 nm and inherited the orientation of the original silicon substrate. Deposited Cu nanoparticles were found to be partially oxidized to Cu₂O while CuO was not detected for all samples. In contrast to porous silicon, the crystal orientation of the original silicon substrate significantly affected the sizes, density, and oxidation level of Cu nanoparticles deposited on bulk silicon.     

The effect of etching temperature on the photoluminescence emitted from, and the morphology of, p-type porous silicon

The temperature at which silicon is electrochemically etched has been found to influence the structure and photoluminescence properties of porous silicon. Decreasing the temperature increased both the current efficiency of the dissolution process and the porosity of the resulting porous layer. Furthermore, a blue-shift was observed in the photoluminescence indicating that the decreased temperature allowed smaller nanocrystals to be formed. An analysis of temperature dependence of the pore initiation and propagation models currently available in the literature failed to yield a satisfactory explanation for the decrease in the average size of the nanocrystals indicated by the results presented in the present paper. Therefore it was proposed that at lower temperature smaller nanocrystals are stabilized due to a combination of their reduced solubility and the increased viscosity of the diffusion layer that leads to a higher localized concentration of silicon ions, thereby allowing smaller nanocrystals to be in equilibrium with their surroundings. The fact that previous authors did not observe blue-shifting highlights the importance of the composition of the etching solution in controlling the quality of the porous silicon produced.     

Thermally promoted addition of undecylenic acid on thermally hydrocarbonized porous silicon optical reflectors

Thermally promoted addition of undecylenic acid is studied as a method for modifying porous silicon optical reflectors that have been pre-treated with thermal hydrocarbonization. Successful derivatization of undecylenic acid is demonstrated and confirmed with Fourier transform infrared and X-ray photoelectron spectroscopies. The results indicate that the hydrocarbonization pre-treatment considerably improves stability against oxidation and chemical dissolution in basic environments. The two-step treatment also does not cause an appreciable change on sample reflectance spectra, which enables the use of the functionalized structures in optical sensing applications.     

Hybrid nanostructure of polypyrrole and porous silicon prepared by galvanostatic technique

Nanostructured porous silicon (PS) layer is prepared in a lightly doped p-type substrate (with pores < 5 nm) and used as a working electrode to deposit conducting polypyrrole (PPy) by the electrochemical oxidative polymerization technique in an organic liquid phase. Three distinguishable stages of PPy deposition are observed and recorded under constant applied current: nucleation of polymer at the pore bottom, unidirectional growth of PPy inside the pores, and polymerization outside the PS surface. The hybrid nanostrucutre of PS/PPy shows a significant improvement of electrical conductivity as opposed to the unmodified PS layer. The improved conductivity is observed in spite of the formation of insulating layer of silicon oxides as detected by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) measurements. Systematic study of fabrication and characterization of this organic-inorganic heterosystem, quantification of the PPy in the PS matrix, and the mechanism of filling the nanopores with polymer are presented and thoroughly discussed.     

Submicron machining and biomolecule immobilization on porous silicon by electron beam

Three-dimensional submicrometric structures and biomolecular patterns have been fabricated on a porous silicon film by an electron beam-based functionalization method. The immobilized proteins act as a passivation layer against material corrosion in aqueous solutions. The effects'' dependence on the main parameters of the process (i.e., the electron beam dose, the biomolecule concentration, and the incubation time) has been demonstrated.     

Fabrication,microstructural characterization and gas permeability behavior of porous silicon nitride ceramics with controllable pore structures

Porous Si₃N₄ ceramics with monomodal and bimodal pore structure were prepared by cold isostatic pressing and freeze-casting, respectively. Both the pore structure and permeability behavior of the porous Si₃N₄ ceramics were tailored by altering the pressure of cold isostatic pressing and the composition and content of solvent during freeze-casting. The specimens obtained by cold isostatic pressing exhibited smaller Darcian and non-Darcian permeability than those of freeze-casted samples due to their lower open porosity, smaller pore size and higher tortuosity. On the other hand, compared with the ice-templated specimens having the same solvent volume in the ceramic slurries as them during freeze-casting, the emulsion-ice templated samples showed smaller open porosity, macropore size and Dacian permeability, but the similar non-Darcian permeability because of their larger micropores and better pore interconnectivity.     

Immobilization of peroxidase enzyme onto the porous silicon structure for enhancing its activity and stability

In this work, a commercial peroxidase was immobilized onto porous silicon (PS) support functionalized with 3-aminopropyldiethoxysilane (APDES) and the performance of the obtained catalytic microreactor was studied. The immobilization steps were monitored and the activity of the immobilized enzyme in the PS pores was spectrophotometrically determined. The enzyme immobilization in porous silicon has demonstrated its potential as highly efficient enzymatic reactor. The effect of a polar organic solvent (acetonitrile) and the temperature (up to 50°C) on the activity and stability of the biocatalytic microreactor were studied. After 2-h incubation in organic solvent, the microreactor retained 80% of its initial activity in contrast to the system with free soluble peroxidase that lost 95% of its activity in the same period of time. Peroxidase immobilized into the spaces of the porous silicon support would be perspective for applications in treatments for environmental security such as removal of leached dye in textile industry or in treatment of different industrial effluents. The system can be also applied in the field of biomedicine.     

Photocatalytic activity of Cr-doped TiO2 nanoparticles deposited on porous multicrystalline silicon films

This work deals with the deposition of Cr-doped TiO₂ thin films on porous silicon (PS) prepared from electrochemical anodization of multicrystalline (mc-Si) Si wafers. The effect of Cr doping on the properties of the TiO₂-Cr/PS/Si samples has been investigated by means of X-ray diffraction (XRD), atomic force microcopy (AFM), photoluminescence, lifetime, and laser beam-induced current (LBIC) measurements. The photocatalytic activity is carried out on TiO₂-Cr/PS/Si samples. It was found that the TiO₂-Cr/PS/mc-Si type structure degrades an organic pollutant (amido black) under ultraviolet (UV) light. A noticeable degradation of the pollutant is obtained for a Cr doping of 2 at. %. This result is discussed in light of LBIC and photoluminescence measurements.     

Highly flexible method for the fabrication of photonic crystal slabs based on the selective formation of porous silicon

ABSTRACT: A novel fabrication method of Si-photonic slabs based on the selective formation of porous silicon is reported. Free standing square lattices of cylindrical air holes embedded in a Si matrix can be achieved by proton beam irradiation followed by electrochemical etching of Si wafers. The Photonic Band structures of these slabs show several gaps for the two symmetry directions for reflection through the z-plane. The flexibility of the fabrication method for tuning the frequency range of the gaps over the near and mid infrared ranges is demonstrated. This tuneability can be achieved by simply adjusting the main parameters in the fabrication process such as the proton beam line spacing, proton fluence or anodization current density. Thus, the reported method opens a promising route towards the fabrication of Si-based photonic slabs, with high flexibility and compatible with the current microelectronics industry.     

Correlations of electrochemical behavior, microstructure and chemical composition of porous silicon

Porous silicon (PSi) layers were prepared by anodic polarization of heavily doped n-type Si in hydrofluoric acid-ethanol solutions under varying current densities and etching time. PSi nanocrystallites formed were examined under a high-resolution transmission electron microscope and analyzed by the broadening and red shifting of characteristic Si Raman band. The Raman data were used to calculate the average sizes and distortion angles of crystallites. The chemical compositions of PSi were studied by Fourier transform infrared spectroscopy, and the amounts of Si hydrides and oxides present on PSi were semi-quantitatively evaluated through the integrations of the corresponding bands. The polarity of Si-H and Si-O bonds caused apparent lattice distortions. The chemical species formed on the steps and (1 1 1) surface of PSi nanocrystallites were well distinguished in infrared bands. The amount of Si_ySiH_x species per unit PSi thickness was found to decrease linearly with the increasing current density. The observed relationships among the electrochemical behavior, microstructure and composition are discussed, and a simplified nanocrystallite model is suggested.     

Surface and interface analysis of nanostructured porous silicon layers fabricated at low temperatures from highly doped silicon substrate: application in optical filters

The influence of low temperature of the electrolyte on the surface and interface of porous silicon and its application in optical devices has been studied. Porous Si–bulk Si interface profile was observed by means of the high resolution SEM images. At low temperatures, a decrease in the interface roughness and an increase in the pore size has been observed. These results were used to fabricate optical filters for UV and visible regions at low temperatures. As compared to the filters fabricated at room temperature an increased optical response is reported for the filters formed at low temperature.     

High resolution TEM and triple-axis XRD investigation into porous silicon formed on highly conducting substrates

The microstructure of thin porous silicon films (∼1 μm) formed potentiostatically on p⁺-type silicon in dilute HF solutions is investigated via high resolution TEM and triple-axis XRD. Average pore diameters were found to increase with increasing etching potential, changing from a mixture of micro- and mesopores to predominately square macropores once oxide growth commences. It is postulated that these square pores result from crystallographic etching. High resolution TEM images revealed that stresses within porous silicon are sufficient to cause lattice distortions of the order of a few percent and that once oxide formation occurs areal defects are generated. Although the high resolution TEM analysis suggests that the lattices of the majority of the nanocrystals are compressed relative to bulk silicon and explanations for this are proposed, the combination of the porous silicon film's high porosity and thinness meant that this could not be confirmed by the more reliable triple-axis XRD measurements. Conversely, the triple-axis XRD revealed that thicker films grown under the same conditions had expanded lattices. The results also highlight the drawbacks of relying solely on high resolution TEM or double-axis XRD data when investigating the nature of lattice distortions.