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.     

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.     

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.     

Pressure dependence of the electrical resistivity of natural cassiterite SnO2 and of undoped and Co-doped nanocrystalline SnO2

The pressure dependence of the electrical resistivity of three different samples of cassiterite, namely natural cassiterite SnO₂, synthetic nanocrystalline SnO₂ (with crystallite size 46?nm) and nanocrystalline Co-doped SnO₂ (with crystallite size 32?nm), has been measured up to 7?GPa at room temperature. The resistivity of natural cassiterite SnO₂ decreases from 2.5?×?10⁴?Ωm at normal pressure and temperature to 1.7?×?10⁴?Ωm at 7.0?GPa. The nanocrystalline SnO₂ has a high resistivity 6.0?×?10⁵?Ωm at normal pressure and temperature and decreases with pressure reaching a value of 2.98?×?10⁵?Ωm at 7?GPa. The activation energy of the electrical conduction of the studied samples were found to be 0.32?eV for the natural SnO₂, 0.40?eV for the nanocrystalline SnO₂ sample and 0.28?eV for the nanocrystalline Co-doped SnO₂. Measurements of the pressure dependence of the electrical resistivity of the Co-doped SnO₂ showed a decrease from 3.60?×?10⁵ to 5.4?×?10⁴?Ωm at 7.0?GPa. We did not observe any pressure-induced phase transition in SnO₂ up to 7?GPa. This study of the high-pressure phase stability of cassiterite corroborates the experimental findings of SnO₂ nanoinclusions in diamonds.     

Effect of cooling rate on size-dependent atomic ordering of CoPt nanoparticles

We report on the effect of cooling rate on the size-dependent atomic ordering of CoPt nanoparticles using aberration corrected high-resolution transmission electron microscopy. It was found that cooling rate plays a crucial role in promoting atomic ordering during the cooling process after annealing. Nanoparticles of ≈3?nm in diameter show the A1-disordered phase after annealing at 873?K for 1?h followed by rapid cooling (110?K/min), while the L1₀-ordered phase is obtained when the cooling rate is slow (1.5?K/min). The disordered phase is also obtained by rapid cooling after annealing at 973?K for 1?h. These results unambiguously indicate that the order–disorder transformation temperature is reduced to a temperature at least lower than 873?K for CoPt nanoparticles smaller than 3?nm in diameter. The slow cooling process promotes the atomic ordering, which resulted in an enhancement of magnetic coercivity as high as 2200?Oe. This study demonstrates that hard magnetic properties of the CoPt nanoparticles can be improved by controlling the cooling rate after heat treatments.     

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.     

Absorption and photoluminescence spectroscopy of Er3+-doped SrAl2O4 ceramic phosphors

A spectroscopic characterization of Er³⁺-doped SrAl₂O₄ phosphor materials synthesized by a solid-state reaction method with Er concentrations varying from 0.1 to 1?mol% has been performed by studying photoluminescence (PL) in the temperature range 10 to 360?K and absorption spectra. PL signals containing five emission bands at 1492, 1529, 1541, 1558, and 1600?nm, respectively, have been observed at room temperature for Er³⁺ transitions in the near infrared region. The samples exhibit a main luminescence peak at 1.54?µm, which is assigned to recombination via an intra-4f Er³⁺ transition. Sharp bands centered at around 378, 488, 521, 651, 980, 1492, and 1538?nm in the absorption spectra can be associated with transitions from ⁴I_15/2 level to ²H_9/2, ⁴F_7/2, ²H_11/2, ⁴F_9/2, ⁴I_11/2, ²H_11/2, and ⁴I_13/2 levels, respectively. The sharp emission peaks and excellent luminescence properties show that SrAl₂O₄ is a suitable host for rare-earth-doped phosphors, which may be suitable for optical applications.     

Nucleation of He bubbles in amorphous FeBSi alloy irradiated with He ions

It is interesting to investigate the formation of He bubbles in amorphous alloys because point defects do not exist in amorphous materials. In the present study, the microstructural evolution of amorphous Fe₇₉B₁₆Si₅ alloy, either irradiated with 5?keV He⁺ ions or implanted with 150?eV He⁺ ions without causing displacement damage, and then annealed at a high temperature, was investigated using transmission electron microscopy (TEM). Vacancy-type defects were formed in the amorphous alloy after irradiation with 5?keV He⁺ ions, and He bubbles formed during annealing the irradiated samples at high temperature. On the other hand, for samples implanted with 150?eV He⁺ ions, although He atoms are also trapped in the free volume, no He bubbles were observed during annealing the samples even up to 873?K. In conclusion, the formation of He bubbles is related to the formation and migration of vacancy-type defects even in amorphous alloys.     

Electrical conductivity of Nd and Ce co-doped Gd2Zr2O7 ceramics

In this study, (Gd_{1? x} Nd _x )₂(Zr_{1? x} Ce _x )₂O₇ (0 ≤ x ≤ 0.5) ceramics have been prepared by pressureless sintering at 1973 K to investigate the influence of Nd and Ce co-doping on their electrical conductivity. The electrical conductivity of the ceramics was investigated by impedance spectroscopy measurements from 723 to 1173 K over the frequency range of 20 Hz to 2 MHz in air. The measured values obey the Arrhenius relation. For each composition, the grain conductivity gradually increases with increasing temperature from 723 to 1173 K. At a given temperature, it gradually decreases with increasing neodymium and cerium contents from x = 0 to 0.3; thereafter, the grain conductivity exhibits a slight increase with further increasing neodymium and cerium contents up to x = 0.5.     

Giant electrocaloric effect of highly (1 0 0)-oriented 0.68PbMg1/3Nb2/3O3–0.32PbTiO3 thin film

PbZr_0.95Ti_0.05O₃ thin film has the highest electrocaloric properties of all the oxide thin films (0.48?K?V^?1). Here, it is shown giant electrocaloric properties in 200?nm (1?0?0)-oriented PMN–PT 68/32 film near the ferroelectric Curie temperature of 146?°C. The results indicate the significance of this system to achieve electrocaloric entropy change and temperature change, up to 32.21?J/kg?°C and 14?K, respectively, in 12?V (i.e. 1.155?K?V^?1) near the Curie point. This exceeds the previous best results obtained in PbZr_0.95Ti_0.05O₃ thin film.     

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.     

Effect of mechanical stress on the absorption band tail of cubic boron nitride thin films synthesized by inductively coupled radio-frequency plasma chemical vapour deposition

Thin films of cubic boron nitride were deposited on silica and Si substrates by inductively coupled radio-frequency plasma chemical vapour deposition (IPCVD) technique using a B₂H₆?+?N₂?+?Ar gas mixture. Cubic phase formation was confirmed by glancing-angle X-ray diffraction studies, which showed reflections up to (311). Fourier-transform infrared (FTIR) spectra also indicated the predominantly cubic nature of the deposited films. The optical properties of the films were studied in the wavelength range 200–1000?nm. Both direct and indirect transitions were found to be present. Mechanical stress in the grain-boundary region of the films seems to contribute significantly to the optical absorption below the band gap. The intercrystalline barrier height (E _b) and the trap state density (Q _t ) were obtained from an analysis of the effects of grain boundaries on the optical properties of the samples.     

Reactive solid-state dewetting

High-temperature annealing in air of thick crystalline silver films deposited on high-purity nickel foils promotes solid-state dewetting, whereas no hole through the film is produced when annealing under high purity argon. Scanning electron microscopy observations of the film surface and of cross-sections reveal that dewetting occurs only if a nickel oxide layer forms at the silver-nickel interface, as a result of oxygen diffusion through the silver film. The main dewetting mechanism over short times (1h 1120K in air) is observed to be the condensation, at the silver-nickel oxide interface, of vacancies into voids which grow towards the free surface of the silver film.     

Surface tension measurement of undercooled liquid Ni-based multicomponent alloys

The surface tensions of liquid ternary Ni–5%Cu–5%Fe, quaternary Ni–5%Cu–5%Fe–5%Sn and quinary Ni–5%Cu–5%Fe–5%Sn–5%Ge alloys were determined as a function of temperature by the electromagnetic levitation oscillating drop method. The maximum undercoolings obtained in the experiments are 272 (0.15T _L), 349 (0.21T _L) and 363?K (0.22T _L), respectively. For all the three alloys, the surface tension decreases linearly with the rise of temperature. The surface tension values are 1.799, 1.546 and 1.357?N/m at their liquidus temperatures of 1719, 1644 and 1641?K. Their temperature coefficients are ?4.972?×?10^–4, ?5.057?×?10^?4 and ?5.385?×?10^?4?N/m/K. It is revealed that Sn and Ge are much more efficient than Cu and Fe in reducing the surface tension of Ni-based alloys. The addition of Sn can significantly enlarge the maximum undercooling at the same experimental condition. The viscosity of the three undercooled liquid alloys was also derived from the surface tension data.     

Thermophysical properties of substantially undercooled liquid Ti-Al-Nb ternary alloy measured by electromagnetic levitation

The thermophysical properties of undercooled liquid alloys at high temperature are usually difficult to measure by experiment. Here, we report the specific heat of liquid Ti₄₅Al₄₅Nb₁₀ ternary alloy in the undercooled state. By using electromagnetic levitation technique, a maximum undercooling of 287?K (0.15 T _L) is achieved for this alloy. Its specific heat is determined to be 32.72?±?2.51?J?mol^?1 K^?1 over a broad temperature range of 1578–2010?K.     

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.     

Effect of crystallization on the surface area of porous Ni-based metallic glass foams

The change of the specific surface area in porous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ metallic glass (MG) upon partial crystallization was investigated. The observed increase in the surface area of the annealed Ni-based MG foams is due to the formation of homogeneously distributed Ni₁₀(Zr,Ti)₇ rod-shape intermetallic phases with nominal diameters around 250?nm and ～800?nm length on the surface of MG struts during the crystallization. For longer annealing, the specific surface area decreases again due to a change of the morphology of the crystals from rod-like to disc-like appearance, thus suggesting an optimum regime for increasing the specific surface area upon isothermal annealing at a given temperature.     

Surface tension of substantially undercooled liquid Ti–Al alloy

It is usually difficult to undercool Ti–Al alloys on account of their high reactivity in the liquid state. This results in a serious scarcity of information on their thermophysical properties in the metastable state. Here, we report on the surface tension of a liquid Ti–Al alloy under high undercooling condition. By using the electromagnetic levitation technique, a maximum undercooling of 324 K (0.19 T _L) was achieved for liquid Ti-51 at.% Al alloy. The surface tension of this alloy, which was determined over a broad temperature range 1429–2040 K, increases linearly with the enhancement of undercooling. The experimental value of the surface tension at the liquidus temperature of 1753 K is 1.094 N m^?1 and its temperature coefficient is ?1.422 × 10^?4 N m^?1 K^?1. The viscosity, solute diffusion coefficient and Marangoni number of this liquid Ti–Al alloy are also derived from the measured surface tension.     

Microstructures and tensile properties of 304 steel with dual nanocrystalline and microcrystalline austenite content prepared by aluminothermic reaction casting

The microstructures of 304 stainless steels with different amounts of nanocrystalline and microcrystalline austenite prepared by an aluminothermic reaction casting, without and with annealing at 1073?K for 8?h, have been investigated by X-ray diffraction, an electron probe micro-analyser, a transmission electron microscope and a scanning electron microscope. The steels, both without and with annealing, consisted of different dual nanocrystalline and microcrystalline austenite combinations and a little nanocrystalline δ ferrite, while the average grain size of the nanocrystalline austenite increased from 19 to 26?nm and volume fraction of the microcrystalline austenite increased from 17 to 30% after annealing. The tensile strength of the steel was dramatically increased from 500 to 1000?MPa and the tensile elongation ratio increased from 8 to 12% after annealing. However, the tensile strength was decreased to 600?MPa and the tensile elongation ratio increased from 12 to 22% after an annealing at 1273?K. The combination of dual nanocrystalline and microcrystalline austenite obtained after the annealing at 1073?K results in the best tensile properties.     

Epifluorescence optical microscopy: a sensitive tool for determining the spatial distribution of europium-dihalide precipitates in KCl : KBr : Eu2+ crystals

The spatial distribution of europium-dihalide-type precipitates in KCl?:?KBr?:Eu²⁺ single crystals annealed at 200°C for long periods of time was determined by epifluorescence optical microscopy. Laue-type patterns and optical spectroscopy were used to test the degree of long-range ordering of the specimens and to monitor the precipitation during annealing, respectively. Precipitates smaller than about 0.08?µm were found (2.84?×?10¹² precipitates cm^?3) all across the host, whereas larger precipitates of about 0.17?µm were found (2.9?×?10⁴ precipitates cm^?1) along certain linear structural singularities of the matrix. These singularities, identified as crystal dislocations, were observed to terminate always either at a triple node of singularities or at the crystal surface, forming a three-dimensional network of crystal singularities (2.0?×?10⁶ singularities cm^?2), identified as the Frank network. The presence of europium exhaustive matrix zones accompanying the observed europium-decorated paths indicates that impurity segregation processes, occurring during annealing, favour the precipitation phenomena.