Synthesis and characterization of nanocrystalline MoBi2Te5 thin films for photoelectrode applications

Molybdenum bismuth telluride thin films have been prepared on clean glass substrate using arrested precipitation technique which is based on self-organized growth process. As deposited MoBi₂Te₅ thin films were dried in constant temperature oven at 110°C and further characterized for their optical, structural, morphological, compositional, and electrical analysis. Optical absorption spectra recorded in the wavelength range 300–800?nm showed band gap (E _g) 1.44?eV. X-ray diffraction pattern and scanning electron microscopic images showed that MoBi₂Te₅ thin films are granular, nanocrystalline having rhombohedral structure. The compositional analysis showed close agreements in theoretical and experimental atomic percentages of Mo⁴⁺, Bi³⁺, and Te^2? suggest that chemical formula MoBi₂Te₅ assigned to as deposited molybdenum bismuth telluride new material is confirmed. The electrical conductivity and thermoelectric power measurement showed that the films are semiconducting with n-type conduction. The fill factor and conversion efficiency was characterized by photoelectrochemical (PEC) technique. In this article, we report the optostructural, morphological, compositional, and electrical characteristics of nanocrystalline MoBi₂Te₅ thin films to check its suitability as photoelectrode in PEC cell.     

Pulsed electrodeposition of soft magnetic CoNiFe films under centrifugal forces

A new technique, pulsed electrodeposition under a centrifugal force, is introduced for the preparation of soft magnetic CoNiFe films. The films have enhanced properties such as a high B _s (magnetic saturation) and a low H _c (coercivity), which are desirable for soft magnetic materials. They are also smoother than films deposited under non-pulsed conditions. It is suggested that the technique could be used to prepare various other materials with desirable properties.     

Reversible phase transition in vanadium oxide films sputtered on metal substrates

Vanadium oxide films, deposited on aluminium (Al), titanium (Ti) and tantalum (Ta) metal substrates by pulsed RF magnetron sputtering at a working pressure of 1.5 x10^?2 mbar at room temperature are found to display mixed crystalline vanadium oxide phases viz., VO₂, V₂O₃, V₂O₅. The films have been characterized by field-emission scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy, and their thermo-optical and electrical properties have been investigated. Studies of the deposited films by DSC have revealed a reversible-phase transition found in the temperature range of 45–49 °C.     

Effect of heat treatment on the NO2-sensing properties of sputter-deposited indium tin oxide thin films

Transparent conducting indium tin oxide (ITO) films were deposited onto glass substrates by radio-frequency magnetron sputtering at 648?K, under an oxygen partial pressure of 1?Pa. The effect of annealing on the electrical properties of the films was studied. Characterization of the coatings revealed an electrical resistivity below 6.5?×?10^??3?Ω?cm. The ITO films deposited at 648?K were amorphous, while the crystallinity improved after annealing at 700?K. The surface morphology examined by scanning electron microscopy appears to be uniform over the entire surface area after annealing. The NO₂-sensing properties of the ITO films were investigated and showed sensitivity at concentrations lower than 50?ppm, at a working temperature of 600?K.     

Morphological and magnetic response of copper-substituted nickel ferrite nanoparticles

Ferrite nanoparticles are interesting materials owing to their unique physical and chemical properties. The metal-doped ferrites have well-defined structures and magnetic response, such as high permeability for a specific frequency range. In this study, copper-substituted nickel ferrite (Ni_1?xCu_xFe₂O₄) nanoparticles with a compositional range of 0?≤?x?≤?0.3 were synthesised through a co-precipitation technique. Metal chlorides were used as precursors and NaOH as a precipitating agent for the growth of ferrite nanoparticles. To minimise the internal stresses and maximise the magnetic response, ferrite nanoparticles were annealed in a furnace at 700°C for 6 h. The structural and magnetic response of Ni_1?xCu_xFe₂O₄ ferrite with different values of x were investigated using Scanning Electron Microscopy (SEM), Fourier Transform Infrared spectroscopy (FT-IR), Vibrating Sample Magnetometer (VSM) and X-ray Diffraction (XRD) techniques. XRD analysis confirmed the formation of cubic spinel structure of single phase for all the compositions. The lattice constant decreased with increase in the value of x. FT-IR study showed two main metal oxygen bonds in the range 500–700 cm^?1 confirming the formation of a single-phase cubic inverse structure of Cu-substituted Ni ferrite. VSM results revealed the formation of ferrimagnetic nanoparticles. The optical and magnetic response of the ferrite nanoparticles changed with Cu content.     

Formation of yittrium oxide in cemented carbides

Rare-earth (RE) elements are helpful in improving the mechanical properties of cemented carbides. In this work, the formation of Y₂O₃ in functionally graded cemented carbides is investigated using transmission electron microscopy. The results indicate that Y₂O₃ can stabilize the Co phase with the face-centred cubic structure (α-Co), since it has a cubic structure similar to the high-temperature Co phase. The α-Co phase has a higher plasticity than ε-Co, and this suggests a possible mechanism for the role of RE elements in toughening cemented carbides.     

Electrical properties of thin films of a-Ga x Te100− x composed of nanoparticles

Thin films of Ga _x Te_{100? x} (x?=?3, 6, 9 and 12) have been synthesized by thermal evaporation. From SEM images, it is observed that all the films contain nanoparticles of sizes varying from 100 to 200?nm. The dc electrical conductivity of the as-deposited films of Ga _x Te_100?x nanoparticles is measured as a function of temperature range from 298 to 383?K, and increases exponentially with temperature. The value of the activation energy, calculated from the slope of ln?σ _dc versus 1000/T plots, is found to decrease with increase in the Ga content. On the basis of the value of the pre-exponential factor σ _o, it is suggested that the conduction is due to thermally assisted tunneling of carriers in localized states near the band edges. The optical measurements suggest an indirect optical band gap in this system. The value of the optical band gap decreases on increasing the Ga concentration.     

Unusual stress behaviour of CeO2-doped diamond-like carbon nanofilms

CeO₂-doped diamond-like carbon (DLC) films with thicknesses of 180–200 nm were deposited by unbalanced magnetron sputtering. When the CeO₂ concentration is in the range 5–8%, the residual compressive stress of the deposited films is reduced by 90%, e.g. from about 4.1 GPa to 0.5 GPa, whereas their adhesion strength increases. These effects are attributed to the dissolution of CeO₂ within the DLC amorphous matrix and a widening interface between the DLC film and the Si substrate, respectively.     

Room temperature ferromagnetism and photoluminescence of nanocrystalline Zn1 − xCoxO thin films prepared by sol–gel MOD

Zn_1???xCo_xO (ZC) [x?=?0, 1, 3, 5, 7 and 9?mol%] thin films were prepared by sol–gel combined metallo-organic decomposition method. The films were deposited on the Si substrate with spin-coating technique and annealed at 600?°C for 3?h. X-ray diffraction pattern shows the formation hexagonal wurtzite phase and distortion (c/a) decreases with increasing Co concentration in ZnO. The average grain size is measured using Scherer relation. Atomic force microscopy is used to confirm the formation of nanograins resulted by the use of polyethylene glycol as surfactant. The photoluminescence was recorded by using He-Cd laser of excitation wavelength 325?nm in wavelength region of 350–650?nm which exhibits some influence of Co doping on the multiplication of defects such as O vacancies, Zn interstitials and grain boundary defects. All thin films show room temperature ferromagnetism except pure ZnO which is diamagnetic and 9?mol% of Co shows paramagnetism. This behaviour is interpreted as due to fluctuations in the magnetic ordering, depending on grain size and site location in grain boundaries or oxygen vacancies.     

An explanation for the low-temperature H evolution peak in hydrogenated amorphous silicon films deposited 'on the edge of crystallinity'

The puzzling existence of a sharp low-temperature (T = 400°C) H evolution peak in compact hydrogenated amorphous silicon (a-Si : H) films deposited 'on the edge of crystallinity' is examined. From infrared absorption and X-ray diffraction (XRD) measurements, we show that none of the standard methods used to explain the existence of this peak in a-Si : H materials is applicable to the present films. From the Si-H wag-mode peak frequency, we postulate the existence of very small Si crystallites contained within the amorphous matrix. While the crystallite volume fraction is too small to be detected by XRD in the as-grown films, crystallization is observed for this material at anneal temperatures as low as 500°C. It is proposed that these crystallites catalyse the crystallization of the remainder of the amorphous matrix upon moderate annealing, enabling H surface desorption and H₂ out-diffusion to the sample surface along newly formed grain boundaries at low anneal temperatures.     

Structural phase transitions in epitaxial SrRuO3 thin films

The microstructural evolution of epitaxial SrRuO₃ thin films from ambient temperature (about 293K) to about 900K has been studied by in-situ transmission electron microscopy. Upon heating from the ambient temperature, the intensities of h, k, 2n+1 and h, -h+2n+1, 0 reflections in selected-area electron diffraction patterns decrease with increasing temperature. Two structural phase transitions were observed at about 673and about 783K, revealed by the vanishing of the h, k, 2n+1 and h,-h+2n+1, 0 reflections respectively. The examination of electron diffraction patterns along several different zone axes, taking into account the possible tilting configurations of RuO₆ octahedra, indicates that, upon heating, the orthorhombic structure of SrRuO₃ transforms into a tetragonal structure at about 673K, and further transforms into a cubic structure at about 783K. Possible structural models for the high-temperature phases are considered.     

Effects of annealing temperature on structural,optical, and electrical properties of antimony-doped tin oxide thin films

Antimony-doped tin oxide (ATO) films, approximately 320 nm in thickness, have been prepared by electron beam evaporation onto glass substrates. The films were annealed at temperatures between 400°C and 550°C in air and their structure and surface morphologies were observed by X-ray diffraction (XRD) and atomic force microscopy (AFM) after the different annealing treatments. XRD patterns of the ATO thin films as-deposited and annealed at 400°C showed that they were amorphous, but annealing beyond 400°C caused the films to become polycrystalline with tetragonal structure and orientated in the (1 1 0) direction. The grain size in the annealed films, obtained from the XRD analysis, was in the range 146–256 Å and this increased with the annealing temperature. The dislocation density, cell volume and strain were found to decrease gradually with increasing annealing temperature. Photoluminescence spectra revealed an intensive blue/violet peak at 420 nm, which increased gradually in height with annealing. It is suggested that an increase in the population of Sb⁺⁵ ions might be the reason for the enhancement of the blue/violet emission. The optical properties of the films were also investigated in the UV-visible-NIR region (300–1000 nm). The optical constants, namely the refractive index n and the extinction coefficient k in the visible region were calculated. The optical energy band gap, as determined by the dependence of the absorption coefficient on the photon energy at short wavelengths, was found to increase from 3.59 to 3.76 eV with annealing temperature.     

Investigations of the optical spectra and local structure for nickel(II) ions in XF2 (X = Mg,Zn) single crystals

A complete diagonalization energy matrix method (CDM) is proposed for 3d ⁸ ions in orthorhombic site (D _{2 h} ) symmetry. As an application, the optical spectra of XF₂ : Ni²⁺ (X = Mg, Zn) is well explained on the basis of both the CDM and the semi-self-consistent field d-orbital (semi-SCF d-orbital) theory. In addition, by establishing the relationship between the optical spectra and local structure, it has been possible to calculate the crystal structure parameters for XF₂:Ni²⁺ from optical measurements on Ni²⁺ ions. The theoretical results are in good agreement with experimental findings.     

Nanocomposite-like structure in an epitaxial CaCu3Ti4O12 film on LaAlO3 (001)

We report the detailed microstructural study of a CaCu₃Ti₄O₁₂ (CCTO) thin film using transmission electron microscopy (TEM). The CCTO thin film studied in this work was deposited on a (001)-oriented LaAlO₃ (LAO) substrate by pulsed-laser ablation and has a high dielectric constant of about 10⁴ at 1?MHz at room temperature; however, the mechanism for such a dielectric property is not yet understood. Plan-view TEM studies show that the CCTO samples have orthogonal domain structures with the edge nearly parallel to either the [100] or the [010] direction of the CCTO. A minor anatase TiO₂ phase was found at the domain boundaries. The CCTO and the TiO₂ phases are separated by an amorphous-like layer that has a thickness of several nanometres. Cross-sectional TEM studies reveal that both CCTO and TiO₂ in the films are c axis oriented with a very sharp interface to the LAO-(001) substrate and possess a unique crystallographic orientation relationship of (001) _CCTO //(001)_{TiO 2} //(001) _LAO and [100] _CCTO //[100] _{TiO 2} //[100] _LAO. The Rutherford back-scattering ion chanelling studies suggest a composition of Ca_1.5Cu₃Ti_5.5O₁₆ for the film, in which the extra calcium, titanium and oxygen form the anatase TiO₂ phase and amorphous calcium oxide layer that separates the CCTO and TiO₂ phases. Such nanocomposite-like structures may provide an important clue to the mechanism of the dielectric property of these films.     

Epitaxial Ni-Al thin films on NaCl using a Ag buffer layer

Epitaxial nanoscale [001] films of Ni _x Al_100-x (x = 62.5) have been prepared by physical vapour deposition on to a thin film of Ag [001] on NaCl (001) faces with occasional hillocks. The Ag film contains numerous dislocations and stacking faults and has a rms surface roughness of 2 nm. The Ni-Al film is ordered in the B2 structure and reveals many dislocations as well as antiphase boundaries between ordered domains. The formation of subgrains in the Ni-Al film results in severe height variations up to 30 nm across the surface. A cross-sectional model for the growth of both films is presented.     

A new allotropic structure of silver nanocrystals nucleated and grown over planar polymer molecules

Polymer molecules of polyvinyl alcohol (PVA) serve as a good Ag⁺?→?Ag⁰ reducer as well as a template to produce Ag⁰ nanocrystals of anisotropic shapes. Thin Ag–PVA films (50–100?µm thick) were prepared by carrying out the reaction in aqueous PVA (under heating conditions) and then spin casting the sample in this shape. A topotactic Ag⁺?→?Ag⁰ reaction and in-situ Ag⁰ growth occur in support over the PVA molecules (as per the local structure and Ag⁰–PVA interactions) of elongated surfaces. The Ag⁰ state is confirmed with 3d _5/2 and 3d _3/2 XPS signals of 368.37 and 374.13?eV binding energies, respectively. As analyzed with X-ray diffraction, it is a new allotrope with an orthorhombic structure, lattice parameters a?=?0.8535, b?=?0.8410?nm and c?=?0.4119?nm, and density ρ?=?9.69?g?cm^?3. On heating in air, the well-known cubic structure develops, a?=?0.4082?nm (ρ?=?10.53?g?cm^?3) after 150°C, whereas a?=?0.4071?nm (ρ?= 10.61?g?cm^?3) after 300°C for 2?h. According to proposed models, it is a vacancy-stabilized allotrope, which evolves from multiply twinned particles.     

Electrical properties and local structure of n-type conducting amorphous indium sulphide

An n-type amorphous chalcogenide, In₄₉S₅₁, having a band gap of 1.9eV, has been found. The conductivity in as-prepared films was ～10^?4?S?cm^?1, which increased to 1?×?10^?1?S?cm^?1 on post-annealing at 125°C in vacuum, accompanied by a reduction in the sulphur content of the films. TEM observations showed the amorphous nature of the films before and after annealing. Both Seebeck and Hall coefficients are negative, indicating that the major carriers are electrons. The Hall mobility can be as large as 26?cm²?V^?1?s^?1 at 300?K. No significant changes to the optical absorption were observed upon annealing. Analysis of the X-ray radial distribution function reveals that the sulphur atoms have four-fold coordination, making the structure more rigid than conventional amorphous chalcogenides in which the chalcogen is alloyed to elements of group IV or V of the periodic table. We tentatively associate the electron carrier generation with the formation of sulphur vacancies.     

Solid-source doping of hydrogenated amorphous silicon

Abstract

Arsenic doping of hydrogenated amorphous silicon (a-Si: H) from a solid source in a remote hydrogen plasma reactor is reported. Arsenic incorporation in the deposited films was directly demonstrated with secondary-ion mass spectrometry, and doping efficiency was determined from d.c. conductivity. The electronic properties of the doped films were indistinguishable from those of conventional r.f. glow discharge deposited a-Si:H. The technique should be applicable to other dopant and alloying elements     

Interfacial defects in YBa2Cu3O7-δ/SrTiO3(0 0 1) heterostructures studied by aberration-corrected ultrahigh-resolution electron microscopy

The microstructure of interfacial defects in YBa₂Cu₃O_7-δ/SrTiO₃(0?0?1) heterostructures has been investigated by aberration-corrected ultrahigh-resolution electron microscopy. We determine that c-axis-oriented YBa₂Cu₃O_7-δ thin films epitaxially grow on SrTiO₃(0?0?1) with two types of interface structure. The coalescence of nucleation sites with different types of interface structure leads to the formation of antiphase domain boundaries in YBa₂Cu₃O_7-δ thin films, which terminate at planar faults with different configurations near the interface. Stand-off misfit dislocations are observed and the dislocation core structure is explored. Based on the interface structure and interfacial defects, the initial growth mode of YBa₂Cu₃O_7-δ thin films on SrTiO₃(0?0?1) is discussed.     

A cubic approximant in the Zn-Mg-Er alloy

A cubic approximant for the icosahedral phase is found in the Zn-Mg-Er system. The preparation of the Zn-Mg-Er ternary phase (the so-called R phase) through quenching and annealing is described in detail. The R phase was found by means of scanning electron microscopy in combination with wavelength-dispersive X-ray analysis. The composition of the R phase varies around Zn₆₃Mg₂₃Er₁₄ in different samples depending on the initial composition. The structure has been studied by a combination of high-resolution transmission electron microscopy (HRTEM) and X-ray powder diffraction. The R phase is cubic with a ₀ = 2.02 nm and crystallizes in the space group F 43m. The close relationship of this phase to the icosahedral phase in the Zn-Mg-Y, RE system (RE = rare earth) is demonstrated through electron diffraction features and HRTEM images.