Electrochemical characterization of vertical arrays of tin nanowires grown on silicon substrates as anode materials for lithium rechargeable microbatteries

Vertical arrays of one-dimensional tin nanowires on silicon dioxide (SiO₂)/silicon (Si) substrates have been developed as anode materials for lithium rechargeable microbatteries. The process is complementary metal-oxide-semiconductor (CMOS) compatible for fabricating on-chip microbatteries. Nanoporous anodized aluminum oxide (AAO) templates integrated on SiO₂/Si substrates were employed for fabrication of tin nanowires resulting in high surface area of anodes. The microstructure of these nanowire arrays was investigated by scanning electron microscopy and X-ray diffraction. The electrochemical tests showed that the discharge capacity of about 400 mA h g⁻¹ could be maintained after 15 cycles at the high discharge/charge rate of 4200 mA g⁻¹.     

Fabrication of highly conductive Ru/a-CNx:H composite films by anode deposit

Ruthenium(0) composite hydrogenated amorphous carbon nitride (Ru/a-CN_x:H) films were deposition on single crystal silicon (1 0 0) substrate by electrochemical deposition technique with acetonitrile as carbon source, and Ru₃(CO)₁₂ as dopant. In the deposited progress, the Si (1 0 0) acted as anode. The relative atomic ratio of Ru/N/C was about 0.28/0.33/1, and Ru nanocrystalline particles about 8 nm were homogeneously dispersed into the amorphous carbon matrix. After doping Ru into a-CN_x:H films, the conductivity of the films were evidently improved and the resistivity drastically decrease from 10⁸ Ω cm to about 100 Ω cm.     

Gas chromatographic separation of hydrogen isotopes on columns packed with alumina,modified alumina and sol–gel alumina

The stationary phase of alumina adsorbents, prepared by different chemical processes, was used to study the separation behaviour of hydrogen isotopes. Three types of alumina, obtained by conventional hydroxide route alumina coated with silicon oxide and alumina prepared by internal gelation process (IGP), were used as packing material to study the separation of HT and T₂ in a mixture at various temperatures. The conventional alumina and silicon oxide coated alumina resolved HT and T₂ at 77 K temperature with different retention times. The retention times on SiO₂ coated columns were found to be higher than those of other adsorbents. However, the column filled with IGP alumina was found to be ideal for the separation of HT and T₂ at 240 K. The peaks were well resolved in less than 5 min on this column.     

Carbon based Si- and Cr-containing thin films: Chemical and nanomechanical properties

Si- and Cr-containing C films were deposited by magnetron sputtering combined with CVD onto silicon wafers. The composition and chemical structure were characterized by X-ray Photoelectron Spectroscopy (XPS) and nanomechanical properties by depth-sensing hardness and scratch techniques.The incorporated Si and Cr are preferentially bonded to carbon, in accordance with simplified thermodynamic calculations and as manifested by the XPS chemical shifts. At relatively high Cr- and low Si-content silicides (Cr_xSi) may also form as indicated by X-ray induced Auger electron spectroscopy. The chromium content in the C–Si–Cr films varied between 1 and 55 at% while the silicon content in the same films between 25 and 0 at%. For comparison two-component films of Si–C and Cr–C were also deposited with Si-content up to 42 at% and Cr-content up to 55 at% by varying the input power of the magnetrons.The nanohardness (H) and reduced modulus (E) were higher for all the films than that of the silicon substrate being 10 GPa, 127 GPa, respectively. Interestingly, the H and E of the three-component CrSiC films were almost invariant of the changes of the components' concentration within the indicated range and varied between 13–16 GPa and 120–140 GPa. H and E values for the two-component Cr–C films were much higher, reaching about 22 GPa and 170 GPa, respectively.     

Anisotropic catalytic activity of the orientation controlled Nd2NiO4 + δ/YSZ hetero-epitaxial system for SOFC cathode

Electrode–electrolyte hetero-epitaxial systems for solid oxide fuel cells (SOFCs) with two different configuration of Nd₂NiO_4 + δ(110)//YSZ(100) and Nd₂NiO_4 + δ(100)//YSZ(110) were successfully fabricated by pulsed laser deposition. Thin films of Nd₂NiO_4 + δ approximately 20 nm thick were grown on a commercial single crystal of YSZ. The preferred two-dimensional diffusion paths of the oxide ions were perpendicular to the substrate for both configurations and showed oxygen reduction capability different from each other. This opens up new research direction focusing on the details of anisotropic catalytic activity of SOFC cathode depending on the crystalline surface.     

Room temperature electrodeposition of photoactive Cd(OH)2 nanowires

Cd(OH)₂ nanowires (NWs) were successfully prepared by room temperature electrogeneration of base using Cd(NO₃)₂ aqueous electrolyte and Anodic Alumina Membrane (AAM) as template. Cd(OH)₂ films have been also deposited on tin-doped indium oxide (ITO) for comparison. SEM analysis shows high quality deposits made of closely packed nanowires (NWs) into AAM and uniform flake-like surface on ITO. XRD analysis reveals that Cd(OH)₂ films on ITO are polycrystalline, while the nanowires grow along the preferential directions [1 0 0] and [1 1 0]. Photoelectrochemical measurements show that Cd(OH)₂ NWs are photoactive materials with indirect and direct band gap of 2.15 and 2.75 eV, respectively.     

Effect of Fluoride or Chloride Ions on the Morphology of ZrO2 Thin Film Grown in Ethylene Glycol Electrolyte by Anodization

0.3 wt % ammonium fluoride (NH₄F) or ammonium chloride (NH₄Cl) was added to ethylene glycol (EG) as an active ingredient for the formation of anodic oxide comprising of ZrO₂ nanotubes (ZNTs) by anodic oxidation of zirconium (Zr) at 20 V for 10 min. It was observed that nanotubes were successfully grown in EG/NH₄F/H₂O with aspect ratio of 144.3. Shorter tubes were formed in EG/NH₄F/H₂O₂. This could be due to higher excessive chemical etching at the tip of the tubes. When fluoride was replaced by chloride in both electrolytes, multilayered oxide resembling pyramids was observed. The pyramids have width at the bottom of 3-4 μm and the top is 1-2 μm with 10.7 μm height. Oxidation of Zr in EG/NH₄Cl/H₂O₂ was rater rapid. The multilayered structure is thought to have formed due to the re-deposition of ZrO₂ or hydrated ZrO₂ on the foil inside pores formed within the oxide layer. XRD result revealed an amorphous structure for as-anodized samples regardless of the electrolytes used for this work.     

Fe-doped SnO2 transparent semi-conducting thin films deposited by spray pyrolysis technique: Thermoelectric and p-type conductivity properties

In this paper, we report structural, electrical, optical, and especially thermoelectrical characterization of iron (Fe) doped tin oxide films, which have been deposited by spray pyrolysis technique. The doping level has changed from 0 to 10 wt% in solution ([Fe]/[Sn] = 0–40 at% in solution). The thermoelectric response versus temperature difference has exhibited a nonlinear behavior, and the Seebeck coefficient has been calculated from its slope in temperature range of 300–500 K. The Hall effect and thermoelectric measurements have shown p-type conductivity in SnO₂:Fe films with [Fe]/[Sn] ≥ 7.8 at%. In doping levels lower than 7.8 at%, SnO₂:Fe films have been n-type with a negative thermoelectric coefficient. The Seebeck coefficient for SnO₂:Fe films with 7.8 at% doping level has been obtained to be as high as +1850 μV/K. The analysis of as-deposited samples with thicknesses ～350 nm by X-ray diffraction (XRD) and scanning electron microscopy (SEM) has shown polycrystalline structure with clear characteristic peak of SnO₂ cassiterite phase in all films. The optical transparency (T%) of SnO₂:Fe films in visible spectra decreases from 90% to 75% and electrical resistivity (ρ) increases from 1.2 × 10^?2 to 3 × 10³ Ω cm for Fe-doping in the range 0–40 at%.     

Fast formation of thick and transparent titania nanotubular films from sputtered Ti

Ti films sputtered on transparent fluorine-doped tin oxide glass substrates were anodized in fluoride-containing organic electrolyte in the presence of H₂O. In this work, anodic TiO₂ nanotubes (ATNs) as long as 9.2 ± 0.3 μm were obtained with high growth rate of 0.64 ± 0.3 μm min^?1. We demonstrated the optimum anodization conditions for ATN growth on foreign substrates, were within the range of 0.3–0.5% (wt) NH₄F, with 3–5% (vol) H₂O at 60 V. XPS and ICP-MS were utilized to elucidate the increase of thickness and volume expansion obtained from the sputtered Ti film to their ATN forms. The ATN films exhibited excellent uniformity and adhesion to the substrates.     

Polarized Raman study on the lattice structure of BiFeO3 films prepared by pulsed laser deposition

Polarized Raman spectroscopy was used to study the lattice structure of BiFeO₃ films on different substrates prepared by pulsed laser deposition. Interestingly, the Raman spectra of BiFeO₃ films exhibit distinct polarization dependences. The symmetries of the fundamental Raman modes in 50–700 cm⁻¹ were identified based on group theory. The symmetries of the high order Raman modes in 900–1500 cm⁻¹ of BiFeO₃ are determined for the first time, which can provide strong clarifications to the symmetry of the fundamental peaks in 400–700 cm⁻¹ in return. Moreover, the lattice structures of BiFeO₃ films are identified consequently on the basis of Raman spectroscopy. BiFeO₃ films on SrRuO₃ coated SrTiO₃ (0 0 1) substrate, CaRuO₃ coated SrTiO₃ (0 0 1) substrate and tin-doped indium oxide substrate are found to be in the rhombohedral structure, while BiFeO₃ film on SrRuO₃ coated Nb: SrTiO₃ (0 0 1) substrate is in the monoclinic structure. Our results suggest that polarized Raman spectroscopy would be a feasible tool to study the lattice structure of BiFeO₃ films.     

Effect of Hg2+doping and of the annealing temperature on the nanostructural properties of TiO2 thin films obtained by sol–gel method

This work is a study of Hg²⁺-doped TiO₂ thin films deposited on silicon substrates prepared by sol–gel method and treated at temperatures ranging between 600 to 1000 °C for 2 h. The structural and optical properties of thin films have been studied using different techniques. We analyzed the vibrations of the chemical bands by Fourier transform infrared (FTIR) spectroscopy and the optical properties by UV–Visible spectrophotometry (reflection mode) and photoluminescence (PL). The X-ray diffraction and Raman spectra of TiO₂ thin films confirmed the crystallization of the structure under the form of anatase, rutile, mercury titanate (HgTiO₃) as a function of the annealing temperature. The observation by scanning electron microscopy (SEM) showed the changing morphology, with respect to nanostructures, nanosheets, nanotubes, with the annealing temperature. The diameters of nanotubes ranged from 50 nm to 400 nm. The photoluminescence and reflectance spectra indicated that these structures should enhance photocatalytic activity.     

Photoelectrocatalytic activity of immobilized Yb doped WO_3 photocatalyst for degradation of methyl orange dye

Pure WO_3 and Yb:WO_3 thin films have been synthesized by spray pyrolysis technique. Effect of Yb doping concentration on photoelectrochemical, structural, morphological and optical properties of thin films are studied. X-ray diffraction analysis shows that all thin films are polycrystalline nature and exhibit monoclinic crystal structure. The 3 at% Yb:WO_3 film shows superior photoelectrochemical(PEC) performance than that of pure WO_3 film and it shows maximum photocurrent density(Iph= 1090 μA/cm~2) having onset potentials around +0.3 V/SCE in 0.01 M HClO_4. The photoelectrocatalytic process is more effective than that of the photocatalytic process for degradation of methyl orange(MO) dye. Yb doping in WO_3 photocatalyst is greatly effective to degrade MO dye. The enhancement in photoelectrocatalytic activity is mainly due to the suppressing the recombination rate of photogenerated electron-hole pairs. The mineralization of MO dye in aqueous solution is studied by measuring chemical oxygen demand(COD) values.     

Fast speed nano-sized macropore formation on highly-doped n-type silicon via strong oxidizers

The growth of nano-sized macropores at high speed is studied in this work. Nice macropores with diameters of 60–100 nm and aspect ratio up to 2500 were formed by anodic etching on highly-doped n-type silicon without illumination. The HF-containing electrolytes were modulated with strong oxidizer, H₂O₂, which was also attempted by a few other researchers, but did not lead to the expected macropore formation. Our findings reveal that the pore morphology and etching speed are on dependence of HF concentration and the applied current density. The parameter window of macropore formation, corresponding to the HF concentration ranging from 33% to 67% (by volume) in our experiment, is rather large. In addition, the growth speed can be driven up to 1800 μm/h, while the pores are straight, cylindrical and rather smooth. The current-burst-model is applied to interpret the mechanism of such nano-sized macropore formation.     

Spray deposited amorphous RuO2 for an effective use in electrochemical supercapacitor

The structural, surface morphological and optical properties of sprayed ruthenium oxide thin film were investigated using XRD, SEM and optical absorption measurements. The structural analysis from XRD pattern showed the formation of RuO₂ in amorphous phase. The scanning electron micrographs revealed network-like morphology of ruthenium oxide. The optical studies showed a direct band gap of 2.4 eV for ruthenium oxide films. Ruthenium oxide thin film exhibited a cyclic voltammogram indicative high reversibility of a typical capacitive behavior in 0.5 M H₂SO₄ electrolyte. A specific capacitance of 551 F/g was obtained with ruthenium oxide thin film (electrode) prepared by spray pyrolysis method. The specific capacitances of 551 and 450 F/g at the scan rate of 5 and 125 mV/s, respectively, indicate that the capacitance value varies inversely with scan rate.     

Small-angle X-ray scattering from nano-Si embedded a-SiC:H deposited by hot-wire chemical vapor deposition

Nanocrystalline silicon (nc-Si) embedded a-SiC:H films were deposited by hot-wire chemical vapor deposition (HWCVD) using SiH₄, CH₄ and H₂ gas precursors. The films were characterized by small-angle X-ray scattering, X-ray diffraction (XRD) and Raman spectroscopy to analyze their structural and fractal nature. The analysis of a-SiC:H films indicated the scattering from mass fractal aggregates of amorphous and nanocrystalline domains of nano-Si. The XRD results indicated that the size and crystallite fraction of nanocrystallites decreased with increasing CH₄ flow rate. Nc-Si changed from the mass fractal to the surface fractal with increasing CH₄ flow rate. The inter-diffusion correlation length between nc-Si embedded a-SiC:H varies from 2.4 nm to 5.7 nm with a CH₄ flow rate.     

Controlling macropore formation in patterned n-type silicon: Existence of a pitch-dependent etching current density lower bound

Experimental results on back-side illumination electrochemical etching of patterned (hole square-lattices with pitch p from 2 to 50 μm) n-type silicon substrates in HF-based electrolytes are reported. Experiments reveal the existence of a threshold current density J_pitch, which is strictly correlated to the pattern pitch, above which pore formation can be finely controlled beyond commonly accepted state-of-the-art rules. For instance, using the same silicon substrate, pore array with density D spanning over two orders of magnitude (from 0.0025 μm^? 2 up to of 0.25 μm^? 2) can be etched above a minimum porosity P_min, and, in turn, a minimum pore diameter d_min, which depends on the pattern pitch. Etching current densities below such a critical value give rise to uncontrolled pore growth. The occurrence of the threshold current density J_pitch is interpreted in terms of current burst model.     

Computational simulations of pore nucleation in silicon(1 1 1)

Float zone n-Si(1 1 1) was electrochemically etched in diluted NH₄F to form porous nuclei. The experimental results were compared with computational simulations of pore nucleation and growth. Electrochemical etching of silicon(1 1 1) results in pore nucleation preferentially localized on the edges of atomic terraces. The initial pore nuclei have diameter and depth of 17 nm and 0.3 nm, respectively. We find a correlation between H-terminated Si(1 1 1) atomic surface morphology and electric field distribution on pore nucleation and growth mechanism. The H-terminated surface is composed from wide (100–200 nm) atomic terraces with steps of 0.3 nm height. Electric field enhancement occurs at the terrace edges leading to focusing the holes trajectories. This leads to weakening of the Si–Si backbonds resulting in easy atom removing. The maximum electric field was observed at terrace edges and at the semispherical pore bottom.     

Crystallization of the anodic oxide on titanium in sulphuric acids solution at a very low potential

Anodic oxide films were formed on the deposited pure titanium in 0.1 M H₂SO₄ solution at 30 °C by using cyclic voltammetry (CV) anodization technique. Clear atomic images and step-terrace structure were observed on it by using STM, which gave a direct evidence for the local crystallinity of the anodic oxide films, even though the maximum anodization potential (E_max) was −50 mV, which was much lower than the lowest potential for crystallization in literatures. Moreover, the crystalline degree of the whole anodic oxide film was estimated from the refractive index (n), and the results showed that the crystalline degree increased with potentials. The analysis of XPS spectra revealed that high potentials were also beneficial for the formation of TiO₂, which was the primary substance for the formation of stable crystals in the oxide films.     

Direct electrodeposition of PbTe thin films on n-type silicon

High quality lead telluride thin films were directly deposited onto n-type silicon (1 0 0) substrates by electrodeposition at room temperature. The deposition mechanism was studied using cyclic voltammetry. The films were characterized by scanning electron microscopy, energy dispersive X-ray, X-ray diffraction, and Fourier transform infrared spectroscopy. The results indicated that the deposited PbTe films exhibited a polycrystalline rock salt structure and good optical properties with a direct band gap of 0.31 eV.     

Synthesis of nanoporous activated iridium oxide films by anodized aluminum oxide templated atomic layer deposition

Iridium oxide (IrOx) has been widely studied due to its applications in electrochromic devices, pH sensing, and neural stimulation. Previous work has demonstrated that both Ir and IrOx films with porous morphologies prepared by sputtering exhibit significantly enhanced charge storage capacities. However, sputtering provides only limited control over film porosity. In this work, we demonstrate an alternative scheme for synthesizing nanoporous Ir and activated IrOx films (AIROFs). This scheme utilizes atomic layer deposition to deposit a thin conformal Ir film within a nanoporous anodized aluminum oxide template. The Ir film is then activated by potential cycling in 0.1 M H₂SO₄ to form a nanoporous AIROF. The morphologies and electrochemical properties of the films are characterized by scanning electron microscopy and cyclic voltammetry, respectively. The resulting nanoporous AIROFs exhibit a nanoporous morphology and enhanced cathodal charge storage capacities as large as 311 mC/cm².