Synthesis of nano-structured 3C-SiC by carbothermal reduction of silicon bearing gel and carbon soot

Nano-sized 3C-SiC was synthesized using sol-gel method. The silica bearing sol was prepared using fumed silica and alkaline ethylene glycol which on hydrolysis resulted in a gel. The gel was mixed with nano-sized carbon particles (obtained from soot) and heat treated in 1300-1580 °C temperature range. The formation of 3C-SiC began at ~ 1400 °C and at 1580 °C it was observed to be the major phase while small amount of 2H-SiC was also present. The silicon carbide synthesized between 1400 and 1580 °C had particles in 30-50 nm range and crystallite size between 15 and 17 nm.     

Temperature dependent microstructure of MTES modified hydrophobic silica aerogels

Hydrophobic silica aerogels were prepared using a single step sol-gel process followed by ethanol supercritical drying. Using tetraethoxysilane (TEOS) as a precursor and ammonium hydroxide as a catalyst the aerogel surface was chemically modified with methyltriethoxysilane (MTES). A MTES/TEOS molar ratio of 0.5 (M5) was used. The microstructure of the surface modified aerogels was evaluated as a function of heat treatment temperature over a range of 200-500 °C. The thermal stability was analyzed by simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC) and the microstructure was evaluated by physisorption analysis (BET) and scanning electron microscopy (SEM). The chemical composition and hydrophobicity/hydrophilicity of the aerogels were investigated by Fourier Transform-Infrared (FT-IR) spectroscopy. The M5 aerogels, which were initially hydrophobic, exhibited partial hydrophilicity at treatments above 244.5 °C and complete hydrophilicity above 429.9 °C. The surface area of the aerogels ranged from 776.65-850.20 m²/g. Pore size increased after heat treatment, ranging from 16.25 to 18.52 nm vs. an initial pore size of 14.71 nm. The maximum pore size of 18.52 nm was found at the lowest heat treatment temperature (~ 200 °C). Heat treatment had a mixed effect on the pore volume, as pore volumes decreased at lower treatments (~ 200-400 °C) and increased at higher heat treatments (~ 450-500 °C) relative to the untreated aerogels. With initial heat treatment the Si-CH₃ group began to oxidize to Si-OH. Aerogels heated above 429.9 °C exhibited hydroxyl polymerization leading to aerogels with large particles and a dense microstructure.     

Hydrogen gas-sensing with bilayer structures of WO3 and Pd in SAW and electric systems

A bi-layer sensor structure of WO₃ (~ 100 nm) with a very thin film of palladium (Pd~ 18 nm) on the top, has been studied for hydrogen gas-sensing application at ~ 80 °C and ~ 120 °C and low hydrogen concentrations (0.025-1%). The structures were obtained by vacuum deposition (first the WO₃ and then the Pd film) onto a LiNbO₃ Y-cut Z-propagating substrate making use of the Surface Acoustic Wave method and additionally (in this same technological processes) onto a glass substrate with a planar microelectrode array for simultaneous monitoring of planar resistance of the structure. A very good correlation has been observed between these two methods — frequency changes in SAW method correlate very well with decreases in the bi-layer structure resistance. The SAW method is faster at the lower interaction temperature such as 80 °C, whereas at an elevated temperature of 120 °C, the electrical planar method is also fast and has a lower limit of detection.     

Preparation and characterization of α-Fe2O3 polyhedral nanocrystals via annealing technique

Polyhedral nanocrystals of α-Fe₂O₃ are successfully synthesized by annealing FeCl₃ on silicon substrate at 1000 °C in the presence of H₂ gas diluted with argon (Ar). Uniformly shaped polyhedral nanoparticles (diameter ~ 50-100 nm) are observed at 1000 °C and gases flow rate such as; Ar = 200 ml/min and H₂ = 150 ml/min. Non-uniform shaped nanoparticles (diameter ~ 20-70 nm) are also observed at an annealing temperature of 950 °C with lower gases flow rate (Ar = 100 ml/min and H₂ = 75 ml/min). Nanoparticles are characterized in detail by field-emission electron microscopy (FE-SEM), energy dispersive X-ray (EDX) and high resolution transmission electron microscopy (HRTEM) techniques. HRTEM study shows well resolved (110) fringes corresponding to α-Fe₂O₃, and selected area diffraction pattern (SADP) confirms the crystalline nature of α-Fe₂O₃ polyhedral nanoparticles. It is observed that polyhedral formation of α-Fe₂O₃ nanocrystals depends upon annealing temperature and the surface morphology highly rely on the gas flow rate inside the reaction chamber.     

Enhancement of SiN-induced compressive and tensile strains in Si free-standing microstructures by modulation of SiN network structures

Strain-induced enhancement of carrier mobility is essential for achieving high-speed transistors. The effects of thermal-annealing (temperature: 400-1150 °C) and ultraviolet (UV) laser-annealing (wavelength: 248 nm, temperature: 30-400 °C) on strain-enhancement in Si-pillars covered with Si₃N₄ stress-liners by plasma-enhanced chemical vapor deposition are investigated. Before annealing, the Si₃N₄ stress-liners induce a tensile strain (~ 0.5%) in Si. After thermal-annealing (> 800 °C), the strain becomes highly compressive (> ~ 0.4%), because of dehydrogenation-induced structural relaxation in Si₃N₄ films. On the other hand, the tensile strain becomes large (>~0.7%) after UV laser-annealing at 400 °C, due to non-equilibrium dehydrogenation in Si₃N₄ films. This strain-enhancement technique is useful for the realization of advanced high-speed three-dimensional transistors.     

Thickness dependence of the amorphous-cubic and cubic-hexagonal phase transition temperatures of GeSbTe thin films on silicon nitride

The crystallization temperature of GeSbTe thin films with thicknesses between 11 and 87 nm on silicon nitride was studied through resistance versus temperature measurements. The amorphous-cubic phase transition occurs at ~ 150 °C for all films thicknesses, whereas the cubic-hexagonal phase transition temperature increases with film thickness, from ~ 200 °C for the 20 nm film to ~ 250 °C for the 87 nm film. The cubic-hexagonal transition occurs gradually for the 11 nm film. Implications for phase-change memory devices are discussed.     

Oxidative annealing of ZnSe/GaAs heterostructures

We annealed ZnSe/GaAs heterostructures in the oxygen atmosphere and investigated structural and optical properties of the forming films using X-ray diffraction and photoluminescence. While highly textured ZnO films were synthesized via low-temperature processing (~ 500 °C), high temperature processing (~ 800 °C) promoted reaction at the film/substrate interface and Zn loss from the film surface resulting in the polycrystalline ZnGa₂O₄ and ZnO₂.     

Structural and electrical properties of BiFeO3 thin films by solution deposition and microwave annealing

Lead-free polycrystalline BiFeO₃ (BFO) thin films were developed using a chemical solution deposition method to deposit the films and the multi-mode 2.45 GHz microwave furnace to optimize the annealing condition of the films. Phase-pure BFO films were obtained at 500 °C-600 °C for 1-5 min with a heating rate of 10 °C/min. The film by microwave annealing (MW) at 550 °C for 5 min exhibited a (012)-preferred orientation with a dense morphology of grain size ~ 294 nm. Its dielectric constant of 96.2, low leakage current density of 2.466 × 10^− 6 A/cm², polarization (2P_r) and coercive field (2E_c) of 0.931 μC/cm² and 57.37 kV/cm, respectively, were improved compared to those by conventional annealing (CA) at the same annealing conditions.     

Ni-Mn hydroxides as new high power electrode materials for supercapacitor applications

The coprecipitation of Ni and Mn hydroxides followed by freeze drying results in the formation of agglomerated 20-30 nm particles of complex hydroxide with spinel-like structure. The thermal decomposition of this hydroxide causes the formation of ilmenite-type complex oxide at T > 300 °C without considerable changes in the Ni and Mn valence states according to X-ray photoelectron spectroscopy data. Further processing at T ≤ 400 °C is accompanied by significant particle intergrowth though their internal structure remains nanostructured. Ni-Mn oxide- and hydroxide-based electrodes revealed a significant reversible electrochemical activity in the alkaline electrolytes and an extended operating voltage window (~ 1.8 V). Ni-Mn ilmenite-based electrode materials demonstrated a low fade rate and high specific electrochemical capacity values at high discharge rates (up to 70 mAh g^− 1 at I = 70 mA cm^− 2) that makes feasible their application in high rate batteries and electrochemical supercapacitors.     

Influence of synthesis procedure on the morphology of bismuth oxide particles

A modified sol-gel procedure, based on the esterification reaction, was used to prepare the Bi₂O₃ precursor, which was then heated to 400 or 500 °C. β-Bi₂O₃ obtained at 400 °C showed well-shaped plate-like particles. The mixture β-Bi₂O₃/α-Bi₂O₃, obtained by prolonged heating at 400 °C, yielded pseudospherical particles having about 100 nm in size and much larger particles, as found by FE SEM. α-Bi₂O₃ obtained at 500 °C consisted of particles of varying shapes and sizes. Vitrification of α-Bi₂O₃ was also observed. XRD showed a small fraction of unidentified phase(s) in these samples. Different microstructures were obtained when the precipitation from aqueous Bi(NO₃)₃ solution with tetramethylammonium hydroxide at pH ∼ 14 was used. The precipitation at pH ∼ 3.5 yielded cloverleaf-like particles of good uniformity, which were assigned to BiOOH (isomorphous with (La_0.26Bi_0.24)Bi_0.5OOH. It was found that these particles were made up of much smaller primary BiOOH particles.     

CdTe thin film solar cells with reduced CdS film thickness

A study was performed to reduce the CdS film thickness in CdTe thin film solar cells to minimize losses in quantum efficiency. Using close space sublimation deposition for CdS and CdTe a maximum efficiency of ~ 9.5% was obtained with the standard CdS film thickness of ~ 160 nm. Reduction of the film CdS thickness to less than 100 nm leads to poor cell performance with ~ 5% efficiency, mainly due to a lower open circuit voltage. An alternative approach has been tested to reduce the CdS film thickness (~ 80 nm) by depositing a CdS double layer. The first CdS layer was deposited at high substrate temperature in the range of 520-540 °C and the second CdS layer was deposited at low substrate temperature of ~ 250 °C. The cell prepared using a CdS double layer show better performance with cell efficiency over 10%. Quantum efficiency measurement confirmed that the improvement in the device performance is due to the reduction in CdS film thickness. The effect of double layer structure on cell performance is also observed with chemical bath deposited CdS using fluorine doped SnO₂ as substrate.     

Growth and characterization of germanium epitaxial film on silicon (001) using reduced pressure chemical vapor deposition

High quality germanium (Ge) epitaxial film is grown directly on silicon (001) substrate using a “three-step growth” approach in a reduced pressure chemical vapor deposition system. The growth steps consist of sequential low temperature (LT) at 400 °C, intermediate temperature ramp (LT-HT) of ~ 6.5 °C/min and high temperature (HT) at 600 °C. This is followed by post-growth anneal in hydrogen at temperature ranging from 680 to 825 °C. Analytical characterizations have shown that the Ge epitaxial film of thickness ~ 1 μm experiences thermally induced tensile strain of 0.20% with a threading dislocation density of < 10⁷ cm^− 2 under optical microscope and root mean square roughness of ~ 0.9 nm. Further analysis has shown that the annealing time at high temperature has an impact on the surface morphology of the Ge epitaxial film. Further reduction in the RMS roughness can be achieved either through chemical mechanical polishing or to insert an annealing step between the LT-HT ramp and HT steps.     

Epitaxial growth and surface morphology of aluminum films deposited on mica studied by transmission electron microscopy and atomic force microscopy

The bulk structure and epitaxial growth of aluminum films deposited on mica substrates by thermal evaporation in a wide temperature range (16-550 °C) in high vacuum were investigated by transmission electron microscopy and transmission electron diffraction. The surface morphology of the films was observed and analyzed by atomic force microscopy. The films prepared at room temperature consist of single crystals having a diameter of 90 ± 40 nm with (111) planes. The surface of the films comprises spherical grains with morphology that is caused by self-shadowing during the deposition. The surface of the films becomes smoother as the temperature increases, and atomically-smooth surfaces with a root-mean-square roughness of about 0.45 nm over an area of 1 μm² are obtained at 250-350 °C. The crystals are oriented randomly along the [111] direction perpendicular to the substrate. The surface of the films consists of larger (> 300 nm) grains with terraces, and the surface becomes rough above 400 °C. Films with well-oriented single crystals along the [111] direction perpendicular to the substrate are obtained above 520 °C. The films grown epitaxially at 520-550 °C are characterized by the isolated grains with a diameter of 1220 ± 450 nm.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Synthesis of nano-particles of anatase-TiO2 and preparation of its optically transparent film in PVA

Anatase-TiO₂ nano-particles have been synthesized by using long-carbon chain carboxylic acid and titanium tetrachloride (TiCl₄). As-prepared powder has been calcined at 500 °C to obtain highly crystalline TiO₂. Broad X-ray diffraction (XRD) pattern of as-prepared as well as calcined powder showed all prominent peaks for tetragonal crystal structure representing anatase-TiO₂. The particle diameter by applying Scherrer formula was found to be about 20 nm. It was possible to load as-prepared particles in poly vinyl alcohol (PVA) for optical studies. Optically transparent film showed sharp absorption band for TiO₂ nano-particles at ∼ 300 nm. Photoluminescence (PL) studies of the solution showed emission wavelength at about 330 nm. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) revealed that the particles in the film have uniform distribution and even for the powder no agglomeration was observed. Thermal analysis (TGA) showed that the stability of host polymer is enhanced. FTIR spectra showed presence of carboxylate functional group in the powder.     

Rapid synthesis of ZnO ellipsoidal nanostructures in large scale and their photoluminescence properties

ZnO ellipsoidal nanostructures with uniform ellipsoidal morphologies have been synthesized using different hydroxide anion precursors by an ultra-fast, facile (90 °C) solution-phase method without the assistance of sonication or any surfactants. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) measurements. Based on the experimental results, a growth mechanism of ZnO nanostructures was proposed. The obtained ZnO nanostructures exhibit a weak UV emission band at ~ 385 nm and a relatively stronger orange emission band at ~ 615 nm. The solution-phase method is simple, convenient for large-scale fabrication of ZnO ellipsoidal nanostructures.     

NH4Cl-assisted low temperature synthesis of anatase TiO2 nanostructures from Ti powder

A simple, low temperature and low cost method, which was based on heating the mixture of Ti and NH₄Cl powders in air at 300 °C, has been developed for the controlled synthesis of anatase TiO₂ nanostructures including irregular nanoparticle aggregates, curved nanowires built up by the oriented attachment of nanoparticles, and nanoplates constructed with nanoparticles. The characterization results from X-ray diffraction and Raman spectra indicated that the as-obtained products were anatase TiO₂. Field emission scanning electron microscope images revealed that the products obtained for 3, 10 and 16 h comprised, in turn, irregular nanoparticle aggregates (8-55 nm), curved nanowires built up by the oriented attachment of nanoparticles (~ 9 nm), and nanoplates constructed with nanoparticles (~ 8 nm).     

Vapor-phase synthesis of a solid precursor for α-alumina through a catalytic decomposition of aluminum triisopropoxide

A new solid precursor, hydrous aluminum oxide, for α-alumina nanoparticles was prepared by thermal decomposition of aluminum triisopropoxide (ATI) vapor in a 500 mL batch reactor at 170-250 °C with HCl as catalyst. The conversion of ATI increased with increasing temperature and catalyst content; it was nearly complete at 250 °C with the catalyst at 10 mol% of the ATI. The obtained precursor particles were amorphous, spherical and loosely agglomerated. The primary particle size is in the range 50-150 nm. The ignition loss of the precursor was 24%, considerably lower than 35% of Al(OH)₃, the popular precursor for alumina particles. Upon calcination of the precursor at 1200 °C in the air with a heating rate of 10 °C/min and a holding time of 2 h, the phase was completely transformed into α. The spherical particles composing the precursor turned worm-like by the calcination probably due to sintering between neighboring particles. The surface area equivalent diameter of the resulting α-alumina was 75 nm.     

Characterization of tetragonal BaTiO3 nanopowders prepared with a new soft chemistry route

Preparation of BaTiO₃ nanopowders (37-42 nm) is carried out by a controlled reconstructive thermal decomposition and crystallization from an amorphous polymeric precursor with polyvinyl alcohol (PVA) and sucrose at 400-600 °C in air. The Rietveld refinement of the XRD profile, processed at 600 °C in 2 h, infers the P4mm tetragonal crystal structure (95% of tetragonality) of the as prepared BaTiO₃ nanopowders, with a = 0.3994 nm and c = 0.4024 nm. A cubic symmetry (Pm3m) of 5% in amount with a = 4.0057 is also detected in addition with tetragonal symmetry. The characteristic tetragonal splitting of 002/200 XRD peaks also supports the tetragonal symmetry (c / a = 1.0075) of the as prepared BaTiO₃ nanopowders. The average particle size (D) of the BaTiO₃ powders, estimated with the help of the specific surface area, measured by BET method, is 39.91 nm. Average D value, calculated by Δ2θ_1 / 2 in the XRD peaks with the Debye Scherrer relation is ∼ 40 nm. TEM study measures the particle size of the BaTiO₃ powders with an average diameter of 37 to 42 nm.     

Preparation of rod-like Sb2S3 dendrites processed in conventional hydrothermal

Large-scale rod-like antimony sulfide (Sb₂S₃) dendrites have been prepared by hydrothermal method using antimony chloride (SbCl₃), citric acid and thioacetamide as raw materials at 160 °C for 12 h. The powder X-ray diffraction pattern shows the Sb₂S₃ crystals belong to the orthorhombic phase with calculated lattice parameters a = 1.120 nm, b = 1.128 nm and c = 0.3830 nm. The quantification of energy dispersive X-ray spectrometry analysis peaks gives an atomic ratio of 2:3 for Sb:S. Transmission electron microscopy micrograph studies reveal the appearance of the as-prepared Sb₂S₃ is dendrites-like which is composed of nanorods with the typical width of 300-500 nm and length of 5-20 µm. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of rod-like Sb₂S₃ dendrites is proposed.