Enhanced physical properties of porous silicon for improved hydrogen gas sensing

In the current communication, porous silicon samples were prepared by pulsed photoelectrochemical etching using a hydrofluoric acid-based solution. The structural and gas-sensing properties of the samples were studied. Apart from the cycle time T and pause time T_off of the pulsed current, a novel parameter, in the shape of the current named ‘delay time T_d’ was introduced. Our results showed that by optimization of delay time, the porosity of samples can be controlled due to the chemical preparation of silicon surface prior to electrochemical anodization. The fourier-transform infrared measurements of porous silicon (PS) layers on Si substrate showed that the typical PS surface was characterized by chemical species like Si–H and Si–O–Si terminations. The two-minute delay before applying electrical current was considered sufficient for the fabrication of higher porosity (83%), more uniform, and more stable structures. The photoluminescence (PL) peak of the optimized sample showed higher intensity than the other samples. An obvious PL blue shift also revealed a change in the crystallographic characteristics of silicon due to quantum confinement effects. Metal–semiconductor–metal diodes with Schottky contacts of nickel were fabricated on PS samples and the potential application of optimized substrates for the improved sensitivity, stability, response time and recovery time of hydrogen gas sensors was subsequently studied.     

Electrical and optical characteristics of porous silicon impregnated with LaF3 by a novel chemical bath technique

The structural, electrical and optical characteristics of porous silicon (PS) due to the impregnation of LaF₃ into PS by a novel chemical-bath deposition (CBD) technique have been investigated in this article. Without removing the PS from the anodization chamber the impregnation with LaF₃ has been done by reacting LaCl₃ with HF in the same chamber at room temperature. The impregnation of LaF₃ was confirmed by the SEM on the cross-section of the LaF₃/PS/Si system and EDX. The modification of PS surface by LaF₃ had direct influence on the electrical and optical properties of PS. Electrical properties of Ag/LaF₃/PS/p-Si/Ag structures were studied through the current-voltage (I-V) and capacitance-voltage (C-V) characteristics. Formation of metal-insulator-semiconductor (MIS) diode was evident whose forward current increased with annealing. A diode factor of about 2.4 has been obtained for the annealed heterostructure indicating a high density of trap states. The C⁻²-V curves of all samples showed negative flat band voltage of around −2 V confirming a large number of fixed positive charges in the LaF₃. The photoluminescence (PL) intensity of the LaF₃-impregnated PS showed aging for the as-deposited samples, but when annealed PS structure recovered the PL intensity. Experimental results show that the optimized chemical bath passivation process for the LaF₃ on porous silicon could enable the porous silicon to be an important material for photonic application.     

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.     

The effect of etching time of porous silicon on solar cell performance

Porous silicon (PS) layers based on crystalline silicon (c-Si) n-type wafers with (1 0 0) orientation were prepared using electrochemical etching process at different etching times. The optimal etching time for fabricating the PS layers is 20 min. Nanopores were produced on the PS layer with an average diameter of 5.7 nm. These increased the porosity to 91%. The reduction in the average crystallite size was confirmed by an increase in the broadening of the FWHM as estimated from XRD measurements. The photoluminescence (PL) peaks intensities increased with increasing porosity and showed a greater blue shift in luminescence. Stronger Raman spectral intensity was observed, which shifted and broadened to a lower wave numbers of 514.5 cm⁻¹ as a function of etching time. The lowest effective reflectance of the PS layers was obtained at 20 min etching time. The PS exhibited excellent light-trapping at wavelengths ranging from 400 to 1000 nm. The fabrication of the solar cells based on the PS anti-reflection coating (ARC) layers achieved its highest efficiency at 15.50% at 20 min etching time. The I-V characteristics were studied under 100 mW/cm² illumination conditions.     

Electrical properties of purified solar grade silicon substrates using a combination of porous silicon and SiCl4

This work investigates the photo-thermal treatment of solar grade (SG) silicon to reduce impurities to a low level suitable for high efficiency low-cost solar cells application. It describes experiment carried out by using a tungsten lamps furnace (rapid thermal processing, RTP) to purify solar grade silicon wafers using a combination of porous silicon (PS) and silicon tetrachloride. This process enables to attract the impurities towards the porous layer where they react with SiCl₄ to form metallic chlorides. The gettering effect was studied using the Hall Effect and the Van Der Pauw methods to measure the resistivity, the majority carrier concentration and mobility. We have obtained a significant improvement of the majority carrier mobility after such thermo-chemical treatment. The gettering efficiency is also evaluated by the relative increase of the minority carrier diffusion length L, measured by the light beam induced current (LBIC) technique.     

On the origin of 1.5 μm luminescence in porous silicon coated with sol–gel derived erbium-doped Fe2O3 films

Sol–gel derived Fe₂O₃ films containing about 10 wt% of Er₂O₃ were deposited on porous silicon by dipping or by a spin-on technique followed by thermal processing at 1073 K for 15 min. The samples were characterized by means of PL, SEM and X-ray diffraction analyses. They exhibit strong room-temperature luminescence at 1.5 μm related to erbium in the sol–gel derived host. The luminescence intensity increases by a factor of 1000 when the samples are cooled from 300 to 4.2 K. After complete removal of the erbium-doped film by etching and partial etching the porous silicon, the erbium-related luminescence disappears. Following this, luminescence at 1.5 μm originating from optically active dislocations (“D-lines”) in porous silicon was detected. The influence of the conditions of synthesis on luminescence at 1.5 μm is discussed.     

银纳米颗粒/多孔硅复合材料的制备与气敏性能研究

采用双槽电化学腐蚀法以电阻率为10-15 Ω·cm的p型<100>晶向的单晶硅片制备了孔径约为1.5 μm, 孔深约为15-20 μm的p型多孔硅, 并以此多孔硅作为基底采用无电沉积法通过调控沉积时间在其表面沉积了不同厚度的银纳米颗粒薄膜. 采用扫描电子显微镜和X 射线衍射仪表征了银纳米颗粒/多孔硅复合材料的形貌和微观结构, 结果表明银纳米颗粒较均匀的分布于多孔硅的表面上且沉积时间对产物的形貌有重要影响. 采用静态配气法在室温下研究了银纳米颗粒/多孔硅复合材料对NH₃的气敏性能. 气敏测试结果表明沉积时间对产物的气敏性能影响较大. 当沉积时间较短时, 适量银纳米颗粒掺杂的多孔硅复合材料由于其较高的比表面积以及特殊的形貌和结构, 对NH₃气体表现出较高的灵敏度、优良的响应/恢复性能. 室温下, 其对50 ppm 的NH₃气体的气敏灵敏度可以达到5.8左右.     

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.     

Effect of pore size on ferroelectric properties of multiferroic BiFeO3 films prepared on porous silicon

The ferroelectric properties of BiFeO₃ (BFO) films spray deposited on porous silicon have been studied. The analysis of XRD and FESEM investigations show that the crystalline strain in the BFO films increases with pore size. The BFO films on porous silicon substrate showed improvement in ferroelectric fatigue behavior, remanent polarization and ferroelectric switching time. A maximum memory window of 5.54 V at 1 MHz and a large remanent polarization (P_r) of 13.1 μC/cm² have been obtained at room temperature. The improvement in the ferroelectric properties of these films has been correlated to the crystalline strain.     

Enhanced visible-light coloration and its mechanism of MoO3 thin films by Au nanoparticles

A new kind of MoO₃/Au film was prepared by depositing Au nanoparticles on the surface of MoO₃ thin film through spin-on coating technique. After cathodic polarization, the MoO₃/Au thin film was found to show enhanced visible-light coloration compared with MoO₃ thin films. The formation of Schottky barrier at the MoO₃/Au interface, and the visible-light coloration mechanism of the MoO₃/Au film are elucidated by the energy band theory based on surface photovoltaic spectroscopy measurements.     

Morphology, luminescence, and electrical resistance response to H2 and CO gas exposure of porous InP membranes prepared by electrochemistry in a neutral electrolyte

Porous InP membranes have been prepared by anodization of InP wafers with electron concentration of 1 × 10¹⁷ cm⁻³ and 1 × 10¹⁸ cm⁻³ in a neutral NaCl electrolyte. The internal surfaces of pores in some membranes were modified by electrochemical deposition of gold in a pulsed voltage regime. Photoluminescence and photosensitivity measurements indicate efficient light trapping and porous surface passivation. The photoluminescence and electrical resistivity of the membranes are sensitive to the adsorption of H₂ and CO gas molecules. These properties are also influenced by the deposition of Au nanoparticles inside the pores.     

Investigations on Pd:SnO2/porous silicon structures for sensing LPG and NO2 gas

P-type porous silicon (PS) structure has been prepared by anodic electrochemical etching process under optimized conditions. Photoluminescence studies of the PS structure show emission at longer wavelengths (red) for the excitation at 365 nm. Scanning electron microscope investigations of the PS surface confirm the formation of uniform porous structure, and the pore diameter have been estimated as 25 μm. Pd:SnO₂/PS/p-Si heterojunction with top gold ohmic contact developed by conventional methods has been used as the sensor device. Sensing properties of the device towards liquefied petroleum gas (LPG) and NO₂ gas have been investigated in an indigenously developed sensor test rig. The response and recovery characteristics of the sensor device at different operating temperatures show short response time for LPG. From the studies, maximum sensitivity and optimum operating temperature of the device towards LPG and NO₂ gas sensing has been estimated as 69% at 180 °C and 52% at 220 °C, respectively. The developed sensor device shows a short response time of 25 and 57 s for sensing LPG and NO₂ gases, respectively. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Study of n type porous GaAs by photoluminescence spectroscopy: Effect of the etching time on the deep levels

Photoluminescence (PL) analysis is used to study porous layers elaborated by electrochemical etching of n⁺ Si-doped GaAs substrate with different etching times. Temperature and power dependence photoluminescence (PL) studies were achieved to characterize the effect of the etching time on the deep levels of the n⁺ Si-doped GaAs. The energy emission at about 1.46 eV is attributed to the band-to-band (B-B) (e-h) recombination of a hole gas with electrons in the conduction band. The emission band is composed of four deep levels due to the complex of (V_AsSi_GaV_Ga), a complex of a (Ga vacancy - donor - As vacancy), a (Si_Ga-V_Ga³⁻) defect or Si clustering, and a (gallium antisite double acceptor-effective mass donor pair complex) and which peaked, respectively, at about (0.94, 1, 1.14, and 1.32 eV). The PL intensity behavior as function of the temperature is investigated, and the experimental results are fitted with a rate equation model with double thermal activation energies.     

The influence of CHx coating on the optical properties of porous silicon

In this work, we report a study on the influence of CH_x thickness layer on optical properties of CH_x/PS/Si structures. The hydrocarbon groups were deposited by plasma of methane–argon mixture.The properties of these structures are investigated by photoluminescence (PL), reflection and spectral response measurements from where a different behavior depending on CH_x layer thickness has been observed.The entire total reflection spectrum is modulated by Fabry–Pérot fringes that are a result of thin film interference. As the CH_x layer thickness increases, the amplitude of the interferences decreases and a positive shift of the maximum peak is observed.The PL spectra from CH_x/PS samples with two CH_x layer thicknesses show more intense luminescence than that observed from PS sample and the existence of an optimum thickness CH_x that gives the maximum PL intensity. The spectral response spectra show the presence of an intense peak at 450 nm. Finally, the results point out the importance of CH_x coating in optoelectronic applications.     

Vibrational study on styrene functionalized porous silicon: A method for determining the relative yield of different grafting routes

A new semi-quantitative method providing the relative efficiency of three different organic functionalization reactions onto porous silicon has been set up, based on infrared absorption data. Compared to previously reported techniques, it enables a direct titration of the grafted molecules. We demonstrated that grafting of Si-styrenyl moieties by ethylaluminium dichloride mediated hydrosilylation of phenylacetylene leads to higher yields than organometallic addition onto either hydrogenated or brominated silicon.     

Experimental study on T2 relaxation time of protons in water suspensions of iron-oxide nanoparticles: Cases of composite nanospheres

The experimental transverse relaxivity r_2,exp of protons in water suspensions of spherical SiO₂ shelled γ‐Fe₂O₃ nanoparticle clusters of different sizes is analyzed based on existing models. It is shown that r_2,exp can be significantly larger than the modelling relaxivity, which may be attributed to nanosphere aggregations.     

The influence of the annealing conditions on the photoluminescence of ion-implanted SiO2:Si nanosystem at additional phosphorus implantation

The influence of P ion doping on the photoluminescence (PL) of the system of nanocrystals in SiO₂ matrix (SiO₂:Si) both without annealing and after annealing at various temperatures (provided before and after additional P implantation) is investigated. The Si and P implantation was carried out with ion energies of 150 keV and doses Φ_Si=10¹⁷ cm⁻² and Φ_P=(0.1–300)×10¹⁴ cm⁻² (current density j3 μAcm⁻²). The system after Si implantation was formed at 1000°C and 1100°C (2 h). For the case of SiO₂:Si system as-implanted by P, the intensity of PL was drastically quenched, but partially retained. As for the step-by-step annealing (at progressively increased temperatures) carried out after P implantation, the sign and degree of doping effect change with annealing temperature. The possible mechanisms of these features are discussed.     

Examining the redox and formate mechanisms for water–gas shift reaction on Au/CeO2 using density functional theory

We perform DFT calculations to investigate the redox and formate mechanisms of water–gas-shift (WGS) reaction on Au/CeO₂ catalysts. In the redox mechanism, we analyze all the key elementary steps and find that the OH cleavage is the key step. Three possible pathways of OH cleavage are calculated: (1) OH_ad^″+*^′→H_ad^′+O_ad^″; (2) H_ad^′+OH_ad^″→H₂(g)+O_ad^″+*^′; and (3) OH_ad^″+OH_ad^″→2O_ad^″+H₂(g) (*′: the free adsorption sites on the oxides; ad′: adsorption on the metal; ad″: adsorption on the oxide, respectively). In the formate mechanism, we identify all the possible pathways for the formation and decomposition of surface formates in the WGS reaction. It is found that there is a shortcoming in the redox and formate mechanisms which is related to surface oxygen reproduction. Four possible pathways for producing surface oxygen are studied, and all the barriers of the four pathways are more than 1 eV. Our results suggest that the processes to reproduce surface oxygen in the reaction circle are not kinetically easy.     

Optimization of the ultrasonic assisted removal of methylene blue by gold nanoparticles loaded on activated carbon using experimental design methodology

The present study was focused on the removal of methylene blue (MB) from aqueous solution by ultrasound-assisted adsorption onto the gold nanoparticles loaded on activated carbon (Au-NP-AC). This nanomaterial was characterized using different techniques such as SEM, XRD, and BET. The effects of variables such as pH, initial dye concentration, adsorbent dosage (g), temperature and sonication time (min) on MB removal were studied and using central composite design (CCD) and the optimum experimental conditions were found with desirability function (DF) combined response surface methodology (RSM). Fitting the experimental equilibrium data to various isotherm models such as Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich models show the suitability and applicability of the Langmuir model. Analysis of experimental adsorption data to various kinetic models such as pseudo-first and second order, Elovich and intraparticle diffusion models show the applicability of the second-order equation model. The small amount of proposed adsorbent (0.01 g) is applicable for successful removal of MB (RE > 95%) in short time (1.6 min) with high adsorption capacity (104–185 mg g⁻¹).     

Influence of annealing temperature on the photoluminescence property of ZnO thin film covered by TiO2 nanoparticles

In this work, ZnO thin films covered by TiO₂ nanoparticles (labeled as TiO₂-ZnO thin films) were prepared by electron beam evaporation. The influence of annealing temperature on the photoluminescence property of the samples was studied. The structures and surface morphologies of the samples were analyzed by X-ray diffraction (XRD) and atomic force microscope, respectively. The photoluminescence was used to investigate the fluorescent properties of the samples. The measurement results show that the ultraviolet emission of ZnO thin films is largely enhanced after they are covered by TiO₂ nanoparticles, while the green emission is suppressed. However, when the annealing temperature is relatively high (≥500 °C), the intensity of ultraviolet emission drops off and a violet emission peak along with a blue emission peak appears. This is probably connected with the atomic interdiffusion between TiO₂ nanoparticles and ZnO thin film. Therefore, selecting a suitable annealing temperature is a key factor for obtaining the most efficient ultraviolet emission from TiO₂-ZnO thin films.