Nitrogen ion induced nitridation of Si(111) surface: Energy and fluence dependence

We present the surface modification of Si(111) into silicon nitride by exposure to energetic N₂⁺ ions. In-situ UHV experiments have been performed to optimize the energy and fluence of the N₂⁺ ions to form silicon nitride at room temperature (RT) and characterized in-situ by X-ray photoelectron spectroscopy. We have used N₂⁺ ion beams in the energy range of 0.2–5.0 keV of different fluence to induce surface reactions, which lead to the formation of Si_xN_y on the Si(111) surface. The XPS core level spectra of Si(2p) and N(1s) have been deconvoluted into different oxidation states to extract qualitative information, while survey scans have been used for quantifying of the silicon nitride formation, valence band spectra show that as the N₂⁺ ion fluence increases, there is an increase in the band gap. The secondary electron emission spectra region of photoemission is used to evaluate the change in the work function during the nitridation process. The results show that surface nitridation initially increases rapidly with ion fluence and then saturates.     

Effect of silane flow rate on structural,electrical and optical properties of silicon thin films grown by VHF PECVD technique

Hydrogenated silicon thin films deposited by VHF PECVD process for various silane flow rates have been investigated. The silane flow rate was varied from 5 sccm to 30 sccm, maintaining all other parameters constant. The electrical, structural and optical properties of these films were systematically studied as a function of silane flow rate. These films were characterized by Raman spectroscopy, Scanning Electron Microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy and UV–visible (UV–Vis) spectroscopy. Different crystalline volume fraction (22%–60%) and band gap (∼1.58 eV–∼1.96 eV) were achieved for silicon thin films by varying the silane concentration. A transition from amorphous to nanocrystalline silicon has been confirmed by Raman and FTIR analysis. The film grown at this transition region shows the high conductivity in the order of 10⁻⁴ Ω⁻¹ cm⁻¹.     

Specific contact resistance and metallurgical process of the silver-based paste for making ohmic contact structure on the porous silicon/p-Si surface of the silicon solar cell

Porous silicon has been considered as a promising optoelectronic material for developing a variety of optoelectronic devices and sensors. In the present study, the electrical properties and metallurgical process of the screen-printed Ag metallization formed on the porous silicon surface of the silicon solar cell have been investigated. The contact structure consists of thick-film Ag metal contact patterned on the top of the porous silicon surface. The sintering process consists of a rapid firing step at 750–825 °C in air ambient. It results in the formation of a nearly perfect contact structure between the Ag metal and porous silicon/p-Si structure that forms the top metalization for the screen-printed silicon solar cells. The SEM picture shows that Ag metal firmly coalesces with the silicon surface with a relatively smooth interfacial morphology. This implies that high temperature fire-through step has not introduced any signs of adverse effect of junction puncture or excessive Ag indiffusion, etc. The three-point probe (TPP) method was applied to estimate the specific contact resistance, ρ _c (Ω-cm²) of the contact structure. The TPP measurement shows that contact structure has excellent ohmic properties with ρ _c = 1.2 × 10⁻⁶ Ω-cm² when the metal contact sintered at 825 °C. This value of the specific contact resistance is almost three orders of magnitude lower than the corresponding value of the ρ _c = 7.35 × 10⁻³ Ω-cm² obtained for the contact structure sintered at 750 °C. This improvement in the specific contact resistance indicates that with increase in the sintering temperature, the barrier properties of the contact structure at the interface of the Ag metal and porous silicon structure improved which in turn results a lower specific contact resistance of the contact structure.     

Surface characterization of GSH-CdTe quantum dots

The surface characterization of CdTe QDs synthesized by a novel procedure using glutathione (GSH), low temperatures (60–90 °C) and K₂TeO₃ as the –Te precursor is reported. Fluorescence of the produced QDs is stable in the pH range 6–13 and QDs inside eukaryotic cells are highly fluorescent. The surface composition of GSH-CdTe QDs with different spectroscopic properties and particle size distributions was determined by XPS. The XPS analysis indicated that the QDs are essentially CdTe, although all nanoparticles contain 12–24% of CdO (and in one case also TeO₂). GSH decomposes with reaction time releasing small amounts of S⁻² ions that react with Cd(Te) to yield Cd(Te)S in a smaller amount than that of CdTe. Finally, the use of QDs in fluorescence mediated immunodetection of bacterial pathogens has been evaluated.     

Synthesis and characterization of mesoporous silicon directly from pure silica sodalite single crystal

Mesoporous silicon granules with high surface area were synthesized directly from pure silica sodalite single crystals, with the starting shape retained. The sodalite single crystals were reduced by a magnesiothermal process in vacuum at 630 °C. The X-ray diffraction patterns indicate the presence of crystal silicon. Transmission electron microscopy studies reveal that the obtained silicon granules are composed of a monocrystalline surface with an island-like mesoporous internal structure. The results of N₂ adsorption and desorption analysis indicate that the surface area is around 308 m² g⁻¹ and the single point pore volume is 0.37 cm³ g⁻¹. The photoluminescence emission centered at 2.7 eV may be due to both an oxidized surface and quantum confinement effects. These results reveal that the silicon granules possess a different microstructure from those of etched silicon films. The present synthetic design correlates the microporous zeolite and mesoporous silicon together and gives a new way for enlarging the structural diversity of porous silicon crystal.     

Microwave assisted hydrothermal synthesis and characterization of ZnO–TNT composites

TiO₂ nanotubes with different contents of ZnO (3–40 wt.% ZnO) have been successfully synthesized by microwave assisted hydrothermal process by using commercial TiO₂-P25 as a precursor. The phase and crystallinity of the obtained ZnO–TNT were analyzed by X-ray Diffraction (XRD). The surface area of the ZnO–TNT was determined by BET method. The effect of the different contents of ZnO on morphology of TiO₂ nanotubes was investigated by SEM and TEM. Optical properties and band gap energy of ZnO–TNT were calculated by using UV–vis DRS spectroscopy and modified Kubelka–Munk equation. Photocatalytic performance of ZnO–TNT was investigated by degradation of rhodamine B (RhB) dye under UV and visible light irradiation. Increasing ZnO content in TNT gradually decreased the diameter and length of nanotubes. Furthermore, addition of 40 wt.% ZnO into the TNT exceeded the saturation limit of ion exchangeability of Zn²⁺ and Na⁺ ions and aggregation of finely dispersed ZnO particles on the surface of TNT were observed. The ZnO–TNT has shown relatively larger band gap energies than that of TiO₂-P25. However, ZnO–TNT has shown considerable increase in photo-activity for degradation of RhB dye in visible light as compared to UV light irradiation.     

Preparation and surface properties of mesoporous silica particles modified with poly(N-vinyl-2-pyrrolidone) as a potential adsorbent for bilirubin removal

The surface of silica particles was modified with polyvinyl pyrrolidone (PVP) through sol–gel process. The different experimental techniques, i.e., thermogravimetric analysis (TGA and DTG), nitrogen adsorption, scanning electron microscopy (SEM), laser diffraction analysis (LDA), fourier transform spectroscopy (FTIR) are used to characterize the pure non-functionalized and functionalized silicas containing different amount of PVP. It was shown that PVP-modified silica samples have well developed porous structure; the values of specific surface area for PVP-modified silicas are in the range of 140–264 m² g⁻¹. While the non-functionalized silica shows the low surface area (S_BET = 40 m² g⁻¹). The BJH analysis showed that PVP can be used as an effective agent to increase an average pore size and total pore volume. The results indicate that PVP functionalized silicas show a potential as effective adsorbents for bilirubin removal compared to other available adsorbents.     

Synthesis of mesoporous silicon directly from silicalite-1 single crystals and its response to thermal diffusion of ZnO clusters

This article describes the preparation of mesoporous silicon granules with a layered structure directly from silicalite-1 single crystals. The silicalite-1 single crystals were thermally reduced in vacuum at 630 °C, with the original shape retained. The samples are confirmed as crystalline silicon by X-ray diffraction and transmission electron microscope. The silicon granule is composed of a monocrystalline surface and polycrystalline layered interior. A surface area of around 66 m² g⁻¹ and the pore size centered at 3.7 nm were obtained from nitrogen porosimetry, BET and BJH analysis. The ZnO clusters have been loaded into the porous silicon granule by thermal diffusion method. The photoluminescence emission centered at 3.44 eV originates from the small particles of ZnO and the band at 2.81 eV may be due to both an oxidized surface and quantum confinement effects. The microstructure in this silicon granule is very different from those in etched samples. The synthetic design demonstrates an interesting way from the microporous zeolite to mesoporous silicon and enlarges the structural diversity of porous silicon crystal.     

Preparation and characterization of porous carbons obtained from mixtures of furfuryl alcohol and phenol–formaldehyde resin

Crosslinked carbon network with interconnected pores were obtained from [furfuryl alcohol (FA) + phenol–formaldehyde resin (PF)] – ethylene glycol (EG) mixtures. The effect of FA/PF weight ratio (W_F/P) on the pore structure of the porous carbons has been systematically investigated. The results showed that porous carbons with controlled pore size could be obtained by varying W_F/P in the polymer system. With W_F/P increased, the average pore size and apparent porosity increased from 11.8 to 127.7 nm and from 40.9 to 51.6%, respectively, and the pore size distribution broadened. The property change of the porous carbons was a result of polymerization dynamics change on curing of resin–glycol mixtures induced by varying W_F/P in the polymer system. Increasing the initial W_F/P led curing reactions to occur at relatively lower temperatures, and the degree of polymerization to increase after heat treatment at 150 °C for 16 h, thus cured bodies with different chemical structures were obtained.     

Broadband down-conversion in Bi–Yb-codoped yttrium and yttrium–aluminum oxides

Comparative study of the broadband down-conversion processes in Bi³⁺–Yb³⁺-codoped yttrium oxide (Y₂O₃) and various yttrium–aluminum oxides (Y₃Al₅O₁₂, YAlO₃ and Y₄Al₂O₉) has been performed from the point of view of search for materials suitable for enhancement of efficiency of silicon solar cells. The studied materials in the form of nanopowders have been synthesized by sol–gel method and characterized by X-ray powder diffraction, scanning electron microscopy and luminescence techniques. Relative down-conversion efficiency for studied materials has been estimated. It was shown that optimal concentration of Yb³⁺ ions should be 2–4 at.% simultaneously with Bi³⁺ ions in the amount of about 1 at.%. Such dopants content provides the highest emission intensity of Yb³⁺ ions in near-infrared when excited into Bi³⁺ ions absorption in ultraviolet. Perspectives of the studied materials for enhancement of silicon solar cells are discussed.     

Effect of nanoporous silicon coating on silicon solar cell performance

The surface modification of silicon solar cells was used for improvement of photovoltaic characteristics of silicon solar cells. A screen-printed solar cell technology is used to fabricate n⁺-p silicon solar cell. Nanoporous silicon (PS) layer on n⁺-type Si wafers or on the frontal surface of (n⁺-p)Si solar cell was formed by electrochemical etching in HF-containing solution. The surface morphology, porosity, spectra of photoluminescence and reflectance of PS layers were analyzed. The photovoltaic characteristics of two silicon solar cell type with and without PS layer (PS/(n⁺-p)Si and (n⁺-p)Si cell) were measured and compared. The spectra of photosensitivity of cells were measured in the wavelength range of 300-1100 nm. An average reflection of the porous silicon layer, fabricated on a polished silicon surface, is decreased to 4%. A remarkable increment of the conversion efficiency by 20% have been achieved for PS/(n⁺-p)Si solar cell comparing to (n⁺-p)Si solar cell without PS layer. The results, related with improving of the performance of PS/(n⁺-p)Si solar cell, have been attributed to the effective antireflection and the wide-gap window role of nanoporous silicon on the silicon solar cell.     

Combustion synthesis of porous titanium microspheres

The synthesis of titanium porous microspheres by a combustion technique was studied under an argon atmosphere by using a TiO₂ − 2.5Mg reactive mixture. The precursor, a fine TiO₂ powder, was thermally treated in the range 600–1300 °C prior to the combustion experiments. TiO₂ microspheres whose diameters were between 10 and 50 μm were obtained from precursor particles annealed in the range 900–1100 °C. A biphase product consisting of Ti and MgO phases was obtained when the TiO₂ microspheres were reduced with Mg. The spherical morphology of the final particles was retained despite the relatively high combustion temperatures (1630–1670 °C) used in this study. Moreover, porous titanium microspheres were obtained when the MgO particles were dissolved using acid leaching. Scanning electron microscopy (SEM) images of the microspheres suggested that the spherical structure contained ∼0.5–2.0-μm-diameter porous windows. The Brunauer–Emmett–Teller (BET) surface area of the Ti microspheres was determined to be 2.8 m² g⁻¹.     

Structural modification and enhanced electron emission from multiwalled carbon nanotubes grown on Ag/Fe catalysts coated Si-substrates

Multiwalled carbon nanotubes and carbon nano-filaments were grown using Fe as the main catalyst and Ag as a co-catalyst by microwave plasma enhanced chemical vapour deposition. In this work we demonstrate the growth behaviour of carbon nanotubes (CNTs) grown on pure Fe-film and Ag–Fe films. We find that using Ag film beneath Fe film significantly abate the catalyst–substrate interactions by acting as a barrier layer as well as enhances the nucleation sites for the growth of CNTs due to the limited solubility with Fe and silicon. Scanning electron microscopy and transmission electron microscopy studies were carried out to image the microstructures of the samples. It was observed that the length of Fe catalyzed CNTs was ∼500 nm and Ag–Fe catalyzed CNTs varied from ∼600 nm to 1.7 μm. Micro Raman spectroscopy confirmed the improved crystalline nature of Ag–Fe CNTs. It was found that I_D/I_G ratio for Fe catalyzed CNTs was ∼1.08 and for Ag–Fe catalyzed CNTs was ∼0.7. The Ag–Fe catalyzed CNTs were found to be less defective as compared to Fe catalyzed CNTs. Field emission measurements using diode configuration, showed that electron emission from Ag–Fe catalyzed CNTs was much stronger as compared to Fe catalyzed CNTs. The threshold field for Ag–Fe catalyzed CNTs was (2.6 V μm⁻¹) smaller as compared to Fe catalyzed CNTs (3.8 V μm⁻¹) and thus shows better emission properties. This enhancement in electron emission mechanism as a result of introduction of Ag underlayer is attributed to the increased emitter sites and improved crystallinity.     

Facile preparation and enhanced photocatalytic H2-production activity of Cu(OH)2 nanospheres modified porous g-C3N4

A facile precipitation approach for the preparation of Cu(OH)₂/g-C₃N₄ composite photocatalysts with good porous structure was developed for the first time. The as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible light (UV–vis) absorbance spectra, photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS). A photocatalytic water splitting reaction on the as-prepared photocatalysts were carried out under visible light irradiation. The results revealed that the prepared samples showed significantly enhanced photocatalytic activity. The optimal Cu(OH)₂ loading content was found to be 0.34 mol%, giving an H₂-production rate of 48.7 μmol h⁻¹ g⁻¹, which is higher 16.5 times than that of pure g-C₃N₄. This high photocatalytic H₂-production activity is attributed to the presence of Cu(OH)₂ clusters on the surface of the porous g-C₃N₄, which efficiently promotes the visible light absorption and separation of photogenerated electron–hole pairs.     

Corrosion behaviour of sol–gel coatings doped with cerium salts on 2024-T3 aluminum alloy

The corrosion behaviour of the sol–gel coatings doped with cerium chloride or cerium nitrate on 2024-T3 aluminum alloy was investigated by using electrochemical impedance spectroscopy (EIS) and immersion tests. The sol–gel matrix was obtained through hydrolysis, condensation of 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetramethoxysilane (TMOS), using diethylentriamine as curing agent. The results indicated that cerium nitrate with concentration of 1 × 10⁻³ mol L⁻¹ in the silane solution was excellent on self-healing for the sol–gel coating, while cerium chloride had no obvious effect. This result suggested that the introduction of Cl⁻ promoted the under-film pitting of 2024-T3 substrate. It was found that Ce(OH)₃ and Ce(OH)₂²⁺ simultaneously existed in the silane solution by X-ray diffraction (XRD) analysis. Ce(OH)₂²⁺ transformed to CeO₂ due to high-temperature curing of sol–gel matrix demonstrated by X-ray photoelectron spectroscopy (XPS) analysis. Therefore, it can be considered that Ce(OH)₃ and CeO₂ played inhibition roles in the corrosion process of the sol–gel coatings.     

High-yield synthesis of carbon nanotube–porous nickel oxide nanosheet hybrid and its electrochemical capacitance performance

This study reports an easy chemical conversion route toward large-scale fabrication of carbon nanotube (CNT)–porous nickel oxide (NiO) hybrid nanocomposites as supercapacitor electrode materials. The electrocapacitive performance of CNT–porous NiO hybrids is evaluated by cyclic voltammetry and galvanostatic charge–discharge measurements. The synthesized CNT–NiO hybrid nanocomposite electrode presents a high specific capacitance of 759 F g⁻¹ at 0.5 A g⁻¹ in 6 M KOH aqueous electrolyte, which is almost twice that of pure NiO nanoparticle (388 F g⁻¹) electrodes and nine times of that of commercial NiO particle (88.4 F g⁻¹) electrodes. Furthermore, good capacitance retention is achieved after 1000 cycles of galvanostatic charge–discharge. The synergistic effects from the pseudocapacitance of porous NiO particles, good electrical conductivity, and open tip CNTs attribute to the high capacitance performance.     

Synthesis and selective gas-sensing properties of hierarchically porous intestine-like SnO2 hollow nanostructures

Hierarchically porous intestine-like SnO₂ hollow nanostructures of different dimension were successfully synthesized via a facile, organic template free, H₂O₂-assisted method at room temperature. The morphology as well as texture (congregated solid sphere, intestine-like solid nanostructure, hollow core–shell one, and intestine-like hollow one) of SnO₂ materials can be controlled by varying H₂O₂ concentration and the size of intestine-like hollow SnO₂ can be tuned in the range of 20–120 nm by changing SnSO₄ concentration. The hierarchically porous intestine-like SnO₂ has high specific surface area (142 m² g⁻¹). The gas-sensing behaviors of the intestine-like SnO₂ material to different gas probes such as ethanol, H₂, CO, methane, and butane have been investigated; among them a high selectivity to ethanol was achieved.     

Mesoporous titanium–manganese dioxide for sulphur mustard and soman decontamination

Titanium(IV)–manganese(IV) nano-dispersed oxides were prepared by a homogeneous hydrolysis of potassium permanganate and titanium(IV) oxo-sulphate with 2-chloroacetamide. Synthesised samples were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy (SEM). These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (HD or bis(2-chloroethyl)sulphide) and soman (GD or (3,3′-dimethylbutan-2-yl)-methylphosphonofluoridate). Mn⁴⁺ content affects the decontamination activity; with increasing Mn⁴⁺ content the activity increases for sulphur mustard and decreases for soman. The best decontamination activities for sulphur mustard and soman were observed for samples TiMn_37 with 18.6 wt.% Mn and TiMn_5 with 2.1 wt.% Mn, respectively.     

Irradiation effects in semiconductor

Samples of crystalline silicon, porous silicon, gallium arsenide and silicon diodes were exposed to 50–80 MeV silicon and oxygen ions in the fluence range of the order of 10¹³ to 10¹⁴ ions/cm². The irradiated samples were characterized to obtain information on the relative concentration and depth distribution of the induced defects. For comparison a few silicon diodes and crystalline silicon samples were also exposed to 6 MeV electrons. The main techniques used for the analysis of silicon samples were low angle X-ray diffraction, photo-luminescence spectroscopy and lifetime of minority carriers, whereas diodes were characterized on the basis of switching parameters. It is observed that a large number of defects are produced in the surface region of each of the irradiated semiconductor sample though the energy deposited in the surface region through electronic loss is three orders of magnitude greater than that of nuclear collisions.     

Specific contact resistance measurements of the screen-printed Ag thick film contacts in the silicon solar cells by three-point probe methodology and TLM method

The specific contact resistance of the screen-printed Ag contacts in the silicon solar cells has been investigated by applying two independent test methodologies such as three-point probe (TPP) and well-known transfer length model (TLM) test structure respectively. This paper presents some comparative results obtained with these two measurement techniques for the screen-printed Ag contacts formed on the porous silicon antireflection coating (ARC) in the crystalline silicon solar cells. The contact structure consists of thick-film Ag metal contacts patterned on the top of the etched porous silicon surface. Five different contact formation temperatures ranging from 725 to 825 °C for few minutes in air ambient followed by a short time annealing step at about 450 °C in nitrogen ambient was applied to the test samples in order to study the specific contact resistance of the screen-printed Ag metal contact structure. The specific contact resistance of the Ag metal contacts extracted based on the TPP as well as TLM test methodologies has been compared and verified. It shows that the extraction procedure based on the TPP method results in specific contact resistance, ρ _c  = 2.15 × 10⁻⁶ Ω-cm² indicating that screen-printed Ag contacts has excellent ohmic properties whereas in the case of TLM method, the best value of the specific contact resistance was found to be about ρ _c  = 8.34 × 10⁻⁵ Ω-cm². These results indicate that the ρ _c value extracted for the screen-printed Ag contacts by TPP method is one order of magnitude lower than that of the corresponding value of the ρ _c extracted by TLM method. The advantages and limitations of each of these techniques for quantitatively evaluating the specific contact resistance of the screen-printed Ag contacts are also discussed.