Nanocomposites of Silicon Oxides and Carbon: Its Study as Luminescent Nanomaterials.

In this work, hybrid structures formed by nanostructured layers, which contain materials, such as porous silicon (PSi), carbon nanotubes (CNTs), graphene oxide (GO), and silicon-rich oxide (SRO), were studied. The PSi layers were obtained by electrochemical etching over which CNTs and GO were deposited by spin coating. In addition, SRO layers, in which silicon nanocrystals are embedded, were obtained by hot filament chemical vapor deposition (HFCVD) technique. Photoluminescence (PL) spectra were obtained from the hybrid structures with which a comparative analysis was completed among different PL ones. The SRO layers were used to confine the CNTs and GO. The main purpose of making these hybrid structures is to modulate their PL response and obtain different emission energy regions in the PL response. It was found that the PL spectra of the CNTs/SRO and GO/SRO structures exhibit a shift towards high energies compared to those obtained from the PSi layers; likewise, the PSi/CNTs/SRO and PSi/GO/SRO structures show a similar behavior. To identify the different emission mechanisms originated by PSi, GO, CNTs, and SRO, the PL spectra were deconvolved. It was found that the Psi/CNTs/SRO and Psi/GO/SRO structures exhibit a PL shift in respect to the PSi layers, for this reason, the modulation of the PL emission of the structures makes these hybrid structures promising candidates to be applied in the field of photonic and electroluminescent devices.

Study of the Effect of Nitric Acid in Electrochemically Synthesized Silicon Nanocrystals: Tunability of Bright and Uniform Photoluminescence.

In this work, we show a correlation between the composition and the microstructural and optical properties of bright and uniform luminescent porous silicon (PSi) films. PSi films were synthesized by electrochemical etching using nitric acid in an electrolyte solution. PSi samples synthesized with nitric acid emit stronger (up to six-fold greater) photoluminescence (PL) as compared to those obtained without it. The PL peak is shifted from 630 to 570 nm by changing the concentration ratio of the HF:HNO3:(EtOH-H2O) electrolyte solution, but also shifts with the excitation energy, indicating quantum confinement effects in the silicon nanocrystals (Si-NCs). X-ray photoelectron spectroscopy analysis shows a uniform silicon content in the PSi samples that emit the strongest PL. High-resolution transmission electron microscopy reveals that the Si-NCs in these PSi samples are about ~2.9 ± 0.76 nm in size and are embedded in a dense and stoichiometric SiO2 matrix, as indicated by the Fourier transform infrared analysis. On the other hand, the PSi films that show PL of low intensity present an abrupt change in the silicon content depth and the formation of non-bridging oxygen hole center defects.

Porous Silicon Gas Sensors: The Role of the Layer Thickness and the Silicon Conductivity.

We studied the influences of the thickness of the porous silicon layer and the conductivity type on the porous silicon sensors response when exposed to ethanol vapor. The response was determined at room temperature (27 ∘C) in darkness using a horizontal aluminum electrode pattern. The results indicated that the intensity of the response can be directly or inversely proportional to the thickness of the porous layer depending on the conductivity type of the semiconductor material. The response of the porous sensors was similar to the metal oxide sensors. The results can be used to appropriately select the conductivity of semiconductor materials and the thickness of the porous layer for the target gas.

Hybrid porous silicon/green synthetized Ag microparticles as potential carries for Ag nanoparticles and drug delivery.

In the present work, the fabrication of hybrid porous silicon/green synthetized Ag microparticles was shown and the potential use as carriers for Ag nanoparticles and drug delivery was explored. Hybrid microparticles were fabricated by incorporating green synthetized Ag nanoparticles into porous silicon matrix. The main physicochemical characteristics of the hybrid systems were studied by several techniques including UV-vis spectroscopy, TEM, SEM, XRD and XPS. The toxicology of these hybrid systems was investigated by cell viability, MTT, and comet assays. In addition, the possibility to aggregate different drug to use as drug delivery system was demonstrated by using florfenicol as drug model, due to its importance in salmon industry. The experimental results showed the potential to use these hybrid systems as carries for drug delivery in salmon industry.

Nitrogen-Doped Carbon Dots Induced Enhancement in CO2 Sensing Response From ZnO-Porous Silicon Hybrid Structure.

In this study, we report a simple method for the fabrication of carbon dots sensitized zinc oxide-porous silicon (ZnO-pSi) hybrid structures for carbon dioxide (CO2) sensing. A micro-/nanostructured layer of ZnO is formed over electrochemically prepared pSi substrates using a simple chemical precipitation method. The hybrid structure was structurally and optically characterized using scanning electron microscopy, X-ray diffraction, fluorescence, and cathodoluminescence after the incorporation of hydrothermally prepared nitrogen-doped carbon dots (NCDs) by drop casting. With respect to the control sample, although all the devices show an enhancement in the sensing response in the presence of NCDs, the optimal concentration shows an increase of ~37% at an operating temperature of 200°C and a response time <30 s. The increment in the CO2-sensing response, upon the addition of NCDs, is attributed to an increase in CO2-oxygen species reactions on the ZnO surface due to an increment in the free electron density at the metal-semiconductor-type junction of NCD clusters and ZnO micro-/nanorods. A significant increase in the sensing response (~24%) at low operating temperature (100°C) opens the possibility of developing very large-scale integrable (VLSI), low operational cost gas sensors with easy fabrication methods and low-cost materials.

Dataset for the comparison of vacuum-treated and as-etched porous silicon samples in terms of the evolution of oxidation at low temperatures.

The development of chemical sensors made from porous silicon is a task that has been addressed for several years. In order to have a reliable sensing material, stability must be guaranteed. Oxidation in silicon degrades the sensing capability. The data presented in this article provides some important insights concerning the treatment of samples that can improve the material stability against oxidation. For this purpose, Fourier Transformed Infrared (FTIR) measurements using an Attenuated Total Reflectance (ATR) additament were employed to extract information concerning oxidation on the samples submitted to different temperatures. Photoluminescent (PL) measurements were also performed on the samples in order to extract information on nanocrystals sizes and their relationship with oxidation.

Time-Resolved Spectroscopy of Ethanol Evaporation on Free-Standing Porous Silicon Photonic Microcavities.

In this work, we have followed ethanol evaporation at two different concentrations using a fiber optic spectrometer and a screen capture application with a resolving capacity of 10 ms. The transmission spectra are measured in the visible-near-infrared range with a resolution of 0.5 nm. Porous Silicon microcavities were fabricated by electrochemistry etching of crystalline silicon. The microcavities were designed to have a localized mode at 472 nm (blue band). Ethanol infiltration produces a redshift of approximately 17 nm. After a few minutes, a phase change from liquid to vapor occurs and the localized wavelength shifts back to the blue band. This process happens in a time window of only 60 ms. Our results indicate a difference between two distinct ethanol concentrations (70% and 35%). For the lower ethanol concentration, the blue shift rate process is slower in the first 30 ms and then it equals the high ethanol concentration blue shift rate. We have repeated the same process, but in an extended mode (750 nm), and have obtained similar results. Our results show that these photonic structures and with the spectroscopic technique used here can be implemented as a sensor with sufficient sensitivity and selectivity. Finally, since the photonic structure is a membrane, it can also be used as a transducer. For instance, by placing this photonic structure on top of a fast photodetector whose photo-response lies within the same bandwidth, the optical response can be transferred to an electrical signal.

Enhancement of Peroxidase Stability Against Oxidative Self-Inactivation by Co-immobilization with a Redox-Active Protein in Mesoporous Silicon and Silica Microparticles.

The study of the stability enhancement of a peroxidase immobilized onto mesoporous silicon/silica microparticles is presented. Peroxidases tend to get inactivated in the presence of hydrogen peroxide, their essential co-substrate, following an auto-inactivation mechanism. In order to minimize this inactivation, a second protein was co-immobilized to act as an electron acceptor and thus increase the stability against self-oxidation of peroxidase. Two heme proteins were immobilized into the microparticles: a fungal commercial peroxidase and cytochrome c from equine heart. Two types of biocatalysts were prepared: one with only covalently immobilized peroxidase (one-protein system) and another based on covalent co-immobilization of peroxidase and cytochrome c (two-protein system), both immobilized by using carbodiimide chemistry. The amount of immobilized protein was estimated spectrophotometrically, and the characterization of the biocatalyst support matrix was performed using Brunauer-Emmett-Teller (BET), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and Fourier transform infrared (FTIR) analyses. Stability studies show that co-immobilization with the two-protein system enhances the oxidative stability of peroxidase almost four times with respect to the one-protein system. Thermal stability analysis shows that the immobilization of peroxidase in derivatized porous silicon microparticles does not protect the protein from thermal denaturation, whereas biogenic silica microparticles confer significant thermal stabilization.

Nanostructured copper/porous silicon hybrid systems as efficient sound-emitting devices.

In the present work, the photo-acoustic emission from nanostructured copper/porous silicon hybrid systems was studied. Copper nanoparticles were grown by photo-assisted electroless deposition on crystalline silicon and nanostructured porous silicon (nanoPS). Both the optical and photo-acoustic responses from these systems were determined. The experimental results show a remarkable increase in the photo-acoustic intensity when copper nanoparticles are incorporated to the porous structure. The results thus suggest that the Cu/nanoPS hybrid systems are suitable candidates for several applications in the field of thermoplasmonics, including the development of sound-emitting devices of great efficiency.

Porous silicon functionalization for possible arsenic adsorption.

Thiol-functionalized porous silicon (PS) monolayer was evaluated for its possible application in As (III) adsorption. Dimercaptosuccinic acid (DMSA) attached to mesoporous silicon via amide bond linkages was used as a chelate for As (III). Two different aminosilanes namely 3-(aminopropyl) triethoxysilane (APTES) and 3-aminopropyl (diethoxy)-methylsilane (APDEMS) were tested as linkers to evaluate the relative response for DMSA attachment. The aminosilane-modified PS samples were attached to DMSA by wet impregnation followed by the adsorption of As (III). Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to identify the functional groups and to estimate the As (III) content, respectively. FTIR spectroscopy confirmed the covalent bonding of DMSA with amide and R-COOH groups on the nanostructured porous surface. XPS confirms the preferred arsenic adsorption on the surface of PS/DMSA samples as compared to the aminosilane-modified and bare PS substrates.

Optical characterization of porous silicon monolayers decorated with hydrogel microspheres.

The optical response of porous silicon (pSi) films, covered with a quasi-hexagonal array of hydrogel microspheres, to immersion in ethanol/water mixtures was investigated. For this study, pSi monolayers were fabricated by electrochemical etching, stabilized by thermal oxidation, and decorated with hydrogel microspheres using spin coating. Reflectance spectra of pSi samples with and without deposited hydrogel microspheres were taken at normal incidence. The employed hydrogel microspheres, composed of poly-N-isopropylacrylamide (polyNIPAM), are stimuli-responsive and change their size as well as their refractive index upon exposure to alcohol/water mixtures. Hence, distinct differences in the interference pattern of bare pSi films and pSi layers covered with polyNIPAM spheres could be observed upon their immersion in the respective solutions using reflective interferometric Fourier transform spectroscopy (RIFTS). Here, the amount of reflected light (fast Fourier transform (FFT) amplitude), which corresponds to the refractive index contrast and light scattering at the pSi film interfaces, showed distinct differences for the two fabricated samples. Whereas the FFT amplitude of the bare porous silicon film followed the changes in the refractive index of the surrounding medium, the FFT amplitude of the pSi/polyNIPAM structure depended on the swelling/shrinking of the attached hydrogel spheres and exhibited a minimum in ethanol-water mixtures with 20 wt% ethanol. At this value, the polyNIPAM microgel is collapsed to its minimum size. In contrast, the effective optical thickness, which reflects the effective refractive index of the porous layer, was not influenced by the attached hydrogel spheres. PACS: 81.05.Rm; 81.16.Dn; 83.80Kn; 42.79.Pw.

ZnO-porous silicon nanocomposite for possible memristive device fabrication.

Preliminary results on the fabrication of a memristive device made of zinc oxide (ZnO) over a mesoporous silicon substrate have been reported. Porous silicon (PS) substrate is employed as a template to increase the formation of oxygen vacancies in the ZnO layer and promote suitable grain size conditions for memristance. Morphological and optical properties are investigated using scanning electron microscopy (SEM) and photoluminescence (PL) spectroscopy. The proposed device exhibits a zero-crossing pinched hysteresis current-voltage (I-V) curve characteristic of memristive systems.

Oxygen absorption in free-standing porous silicon: a structural, optical and kinetic analysis.

Porous silicon (PSi) is a nanostructured material possessing a huge surface area per unit volume. In consequence, the adsorption and diffusion of oxygen in PSi are particularly important phenomena and frequently cause significant changes in its properties. In this paper, we study the thermal oxidation of p+-type free-standing PSi fabricated by anodic electrochemical etching. These free-standing samples were characterized by nitrogen adsorption, thermogravimetry, atomic force microscopy and powder X-ray diffraction. The results show a structural phase transition from crystalline silicon to a combination of cristobalite and quartz, passing through amorphous silicon and amorphous silicon-oxide structures, when the thermal oxidation temperature increases from 400 to 900 °C. Moreover, we observe some evidence of a sinterization at 400 °C and an optimal oxygen-absorption temperature about 700 °C. Finally, the UV/Visible spectrophotometry reveals a red and a blue shift of the optical transmittance spectra for samples with oxidation temperatures lower and higher than 700 °C, respectively.