Hydrothermal synthesis and characterization of VO2 (B) nanorods array

Highly ordered nanorods array of B phase vanadium dioxide was firstly synthesized with n-butanol as the reducing agent via a simple hydrothermal method without using template. The samples have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). The size of VO₂ (B) nanorods has the dimension of 50–100 nm in diameter and about 1–5 μm in length. The samples were measured as electrode materials by charge–discharge technique and the VO₂ (B) nanorods array demonstrated a high specific capacity of 520 mAh/g at 0.2 C. The influence of reaction temperature on fabricating nanorods array has been studied. The possible growth mechanisms of formation of nanorods and assembly of array were discussed.     

Pressure assisted evolution of defects in silicon

The effect of enhanced hydrostatic pressure following heat treatment on the evolution of point defects in neutron‐irradiated Czochralski‐grown silicon is investigated using infrared spectroscopy. The behavior of oxygen‐related defects, particularly of the VO and the VO₂ centers, is mainly studied using samples subjected to heat treatment under hydrostatic pressure. It is observed that (1) pressure accelerates the annealing process of the VO defects and enhances the growth of the VO₂ complexes and (2) the VO₂ concentration is larger than expected from the corresponding decay of the VO defects. The faster decay of the VO defects is attributed to a pressure‐induced decrease of their migration energy. The larger VO₂ concentration is also discussed. One possible explanation is that pressure stimulates an additional mechanism for the formation of the VO₂ defects, which involves the reaction of oxygen dimers with vacancies. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Darstellung von VO2-einkristallen der oberen und unteren phasengrenze durch chemischen transport

The chemical transport of VO₂ with TeCl₄ was investigated in the temperature range of about 1000°C and 600°C. In the first case there is TeO₂ existing in the gaseous phase, in the second case the TeO₂ has no noticeable vapour pressure. The transport takes place from the hot to the cool zone. In both cases we obtained high transport rates of 10 to 20 mg h^-1. The composition of the gaseous phase is calculated and the transport mechanisms are discussed. It is possible to obtain VO₂ with the upper and lower phase boundary by variation of the initial compositions. Starting with compositions lower than VO_1.99 we obtained near 1000°C in the deposition zone V₈O₁₅ first and after a time VO₂ with the lower phase boundary. Compositions higher than VO_2.00 give vanadium dioxide with the upper phase boundary. In the temperature range of about 600°C however we obtained the phase with the higher oxygen content first. The results are compared with those, which have been obtained by the transport of VO₂ with HCl and Cl₂ — which takes place from the cool to the hot zone.     

On the Bindings in VOm Phases

The phenomenological plural correlations model permits to attribute to the intermediate phases of the mixture VO_M bonding types (bindings) which indicate a low energy of the empirically found structures. In the phases various electron subsystems exist which contain lattice-like spatial correlations, and when the corresponding cells are in energetically low commensurabilities (in harmonies) to the crystal and to one another then the phase becomes stable. A fundamental assumption of a binding analysis is the electron count being here V^1,4,8O^0,6,2. As a consequence the phases V₈O, V₁₆O₃, and V₇O₄ consist of a tetra-gonally deformed V(B1) partial structure with interstices partly filled by O atoms. The composition of a phase determines the electron concentrations in the subsystems, and these influence the harmony of the correlations in the binding (BF_U2 for V₁₆O₃, e.g.). In VO, V₁₃O₁₆, V₂O₃, and V₃O₅ an essentially complete close packed partial structure of O accepts V into its octahedral interstices. Once more harmonies of electron correlations determine favourable bindings (FF'2 for VO e.g.). The Magnéli phases V₄O₇ up to V₈O₁₅ being shear homeotypes of VO₂ · h may be considered as homeodesmic to TiO₂ · r, which is stabilized by a CF_U2 binding. From the binding it may be concluded how much Hund insertion is present in a phase. Hund insertion is for instance responsible for the transformation VO₂ · h → r. The phases V₆O₁₃, V₄O₉ and V₃O₇ are homeotypic to V₂O₅. This last phase permits presumably a UH_T3 binding. The results of the binding analysis of VO_M shed some new light on the interpretation of properties of the VO_M phases.     

Low temperature powder diffraction and DFT solid state computational study of hydrogen bonding in NH4VO3

The crystal structure of NH₄VO₃ was refined by the geometry optimization done by total energy minimization in solid state using DFT/plane waves approach. The lattice parameters were derived by the Le Bail technique from the low temperature X‐ray (40‐293 K) and synchrotron (100‐293 K) powder diffraction data. The structure is formed by the infinite chains of irregular VO₄ tetrahedra running approximately parallel to the c‐axis, which are interlinked by the ammonium ions placed between them. The ammonium ions link to the [VO₄]_∞ chains through one linear, one bifurcated and two trifurcated N‐H…O hydrogen bonds. Considering their stability there are six distinct N‐H…O hydrogen bonds: two strong with the N‐H…O bond angles close to the straight, two medium with the bond angles of 123° and 148° and two very bent (105° and 107°) and hence weak hydrogen bonds. There is a reasonable agreement between the energies of the stretching ν(NH) modes estimated using the optimised N…O contact distances and those obtained experimentally. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and spectroscopic study of Mg13.4(OH)6(HVO4)2(H0.2VO4)6

Single‐crystals of the polar compound magnesium hydrogen vanadate(V), Mg_13.4(OH)₆(HVO₄)₂(H_0.2VO₄)₆, were synthesized hydrothermally. It represents the first hydrogen vanadate(V) among inorganic compounds. Its structure was determined by single‐crystal X‐ray diffraction [space group P 6₃mc, a = 12.9096(2), c = 5.0755(1) Å, V = 732.55(2) ų, Z = 1]. The crystal structure of Mg_13.4(OH)₆(HVO₄)₂(H_0.2VO₄)₆ consists of well separated, vacancy‐interrupted chains of face sharing Mg2O₆ octahedra, with short Mg2—Mg2 distances of 2.537(1) Å, embedded in a porous magnesium vanadate 3D framework having the topology of the zeolite cancrinite. All three hydrogen positions in the structure were confirmed by FTIR spectroscopy. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vanadium pentoxide nanobelts: One pot synthesis and its lithium storage behavior

In this paper, we report a synthesis, characterization and electrochemical properties of V₂O₅ nanobelts. V₂O₅ nanobelts have been prepared via hydrothermal treatment of commercial V₂O₅ in acidic (HCl/H₂SO₄) medium at relatively low temperature (160 °C). The hydrothermally derived products have been characterized by powder X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), Raman spectroscopy, X‐ray photo electron spectroscopy (XPS), UV‐Vis spectroscopy, Scanning/Transmission electron microscopy (SEM/TEM). XRD pattern of V₂O₅ nanobelts show an orthorhombic phase. From the FTIR spectrum, the peak observed at 1018 cm⁻¹ is characteristic of the stretching vibration mode of the terminal vanadyl, V = O. The UV‐Vis absorption spectrum of V₂O₅ nanobelts show maximum absorbance at 430 nm, which was blue‐shifted compared to that of bulk V₂O₅. TEM micrographs reveal that the products consist of nanobelts of 40‐200 nm in thickness and several tens of micrometers in length. The electrochemical analysis shows an initial discharge capacity of 360 mAh g⁻¹ and its almost stabilized capacity is reached to 250 mAh g⁻¹ after 55 cycles. A probable reaction mechanism for the formation of orthorhombic V₂O₅ nanobelts is proposed.     

Phase composition,microstructure and conductivity of (85-α)VO2–15(Vanadium–Phosphate–Glass)–αCu glass–ceramics

Electric conductivity, microstructure and phase composition of (85-α)VO₂–15VPG–αCu glass–ceramics (VPG = Vanadium–Phosphate–Glass) with copper content in the interval 0 wt% ⩽ α ⩽ 15 wt% were investigated. VPG is the glass (molar %) 80V₂O₅–20P₂O₅. Only two phases: VO₂ and VPG were identified when α ⩽ 5 wt%. VO₂ crystallites, VPG and pores are observed in these ceramic microstructures. Glass forms layers 1–2 μm thick in the space between VO₂ crystallites. The copper is dissolved in VPG during glass–ceramic synthesis. It increases the electric conductivity of the glass and provides improvement of electrical bonds between VO₂ crystallites. Therefore glass–ceramics conductivity exhibits an abrupt change of approximately 100× in the vicinity of the phase transition temperature, T_t, in VO₂. A new crystalline phase appears in (85-α)VO₂–15VPG–αCu ceramics when α ∼ 6 wt%. This phase is observed as small crystallites with the sizes of 1–5 μm. The increase in such phase content, with an increase in copper content is accompanied by a decrease in the content of VO₂. Percolation along the new phase is a primary contributor to electric conductivity when α ⩾ 8 wt%. In this case the conductivity exhibits no abrupt change in the vicinity of the temperature T_t. The new phase is probably the bronze Cu_xV₂O₄. It crystallizes from a liquid phase during glass–ceramics synthesis.     

Conductivity stabilization by metal and oxide additives in ceramics on the basis of VO2 and glass V2O5–P2O5

Conductivity behavior during the temperature cycling through the phase transition temperature of VO₂ (T_t = 68 °C) was investigated in glass-ceramics based on VO₂ and vanadium phosphate glass (VPG) for compositions without and with Cu and SnO₂ additives. Copper and SnO₂ additives stabilize the conductivity of glass-ceramics at temperature cycling. For ceramics (wt%) (80 − y)VO₂–5Cu–15VPG–ySnO₂ the best stabilizing effect takes place when SnO₂ content is in the interval 35 wt% < y < 50 wt%. Ceramics with such SnO₂ content keeps a stable value of the conductivity change (∼10²) in the vicinity of VO₂ phase transition temperature and shows the conductivity decrease no more than of 2.5 times after 3000 thermal cycles. The reasons of conductivity stabilizing in VO₂-based glass-ceramics with additives of Cu and SnO₂ are being discussed. The analysis resting on the percolation theory has shown the increase of conductivity stability in VO₂-based glass-ceramics when the VO₂ volume fraction and the average size of VO₂ crystallites decrease and the ceramics surface tension increases.     

Thermal conductivity and refractive indices of Nd:GdVO4 crystals

The thermal conductivities of Nd:YAG, M(Y,Gd)VO₄ crystals were measured at 298 K. The value of Nd:GdVO₄ crystal along <001> direction was 11.4 W/mK, which was higher than that of YAG crystal measured to be 10.7 W/mK. The principal refractive indices of Nd:GdVO₄ crystal in the temperature range from 20 °C to 170 °C were determined by auto‐collimation method. Based on the measured values of refractive indices, the Sellmeier equation and expression of temperature dependence of refractive indices have been obtained. The measured results show that the birefringence Δn is 0.22007 at 20 °C and temperature coefficient of birefringence is 4.33 × 10⁻⁶/°C for 1.064 μm. These results prove that the GdVO₄ crystal is a laser crystal with excellent thermal and birefringence properties. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth of mixed‐valence ammonium vanadates

A new method has been developed for the synthesis of mixed‐valence ammonium vanadate crystals. Single crystals of (NH₄)₂V₃O₈ were synthesized on a large scale by hydrothermal reduction of NH₄VO₃ in ethanol‐H₂O solutions in the presence of triblock copolymer Pluronic P123. The crystals are shining thin plates with (001) cleavage planes. Calcination of the (NH₄)₂V₃O₈ crystals at 300°C or above resulted in pure phases of V₂O₅. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Novel electrospun SnO2@carbon nanofibers as high performance anodes for lithium‐ion batteries

SnO₂@carbon (SnO₂@C) nanofibers (NFs) have been prepared by electrospinning method and evaluated as anodes in lithium‐ion battery half cells. XRD were carried out to provide further information about the structure of the as‐prepared NFs, and all the peaks can be readily indexed to the rutile phase SnO₂ (JCPDS No. 41–1445). Electrochemical characterization by galvanostatic charge‐discharge tests shows that the NF anodes have first discharge capacities of 1375.5 mA h g⁻¹ at 80 mA g⁻¹current density. This excellent Li‐ion storage capability of SnO₂ NFs is probably resulting from protection of amorphous carbon and the synergy arising from that the ultrafine SnO₂ particles embedded in the carbon nanofiber (CNF) matrix: the nanometer‐sized SnO₂@C NFs can provide not only negligible diffusion times of ions thus faster phase transitions but also enough space to buffer the volume changes during the lithium insertion and extraction reactions. The highly dispersed NFs are expected to be applied as attractive anodes for lithium‐ion batteries.     

Synthesis and improved electrochemical performance of LiCo1‐xSnxO2 (x= 0 to 0.1) powders

Layered intercalation compounds LiCo_1‐xSn_xO₂ (x= 0 to 0.1) have been prepared using a simple combustion route method. X‐ray diffraction patterns and Laser Raman spectrum suggest that the synthesized materials had the R‐3m structure. Scanning electron images show that particles are well‐crystallized with a size distribution in the range of 50‐100 nm. The room temperature electrical conductivity of the sample increased with Sn content. For LiCo_1‐xSn_xO₂(x = 0, 0.01, 0.03, 0.05 and 0.1), the first discharge capacity increased with increase in Sn content. Among these samples, LiCo_0.95Sn_0.05O₂had produced the best performance of all others with a stable reversible capacity of 186 mAhg^‐1 after 30 cycles. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of vanadium dioxide thin films on conducting oxides and metal–insulator transition characteristics

We report on growth and physical properties of vanadium dioxide (VO₂) films on model conducting oxide underlayers (Nb-doped SrTiO₃ and RuO₂ buffered TiO₂ single crystals). The VO₂ films, synthesized by rf sputtering, are highly textured as seen from X-ray diffraction. The VO₂ film grown on Nb doped SrTiO₃ shows over two orders of magnitude metal–insulator transition, while VO₂ film on RuO₂ buffered TiO₂ shows a smaller resistance change but with an interesting two step transition. X-ray photoelectron spectroscopy has been performed as a function of depth on both sets of structures to provide mechanistic understanding of the transition characteristics. We then investigate voltage-driven transition in the VO₂ films grown on Nb-doped SrTiO₃ substrate as a function of temperature. The present study contributes to efforts towards correlated oxide electronics utilizing phase transitions.     

Low temperature polycrystalline silicon film formation by metal induced crystallization with nickel salt derived by ultrasonic spray pyrolysis

Solution‐based nickel induced crystallization of amorphous silicon (a‐Si) films was performed. The nickel solution was prepared by dissolving (CH₃CO₂)₂Ni in deionized water and applied uniformly on a‐Si films by low‐cost ultrasonic spray pyrolysis method. Crystallization could be realized for a‐Si films coated with a 0.2 M nickel solution and annealed at 500 °C. The effect of substrate temperature during nickel solution deposition was analyzed. Micro‐Raman and x‐ray diffraction measurement show that a‐Si is fully crystallized at 550 °C for 7 h with a nickel concentration of 0.8 M. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temperature‐concentration oscillations of crystal‐solution phase equilibria in the presence of trace impurities of surface‐active agents

Using the examples of aqueous salt solutions NaNO₃, KNO₃, RbNO₃, K₂SO₄, NaBr·2H₂O, KBr, and NH₄NO₃, it was experimentally proven that the new phenomena, i.e. temperature‐concentration oscillations of crystal‐solution phase equilibria detected previously in the range of 15–45 °C remain in the presence of trace impurities (10^‐4–10^‐3 wt. %) of ion‐active organic matters. The signs of breaks transformation into pair oscillations of “maximum‐minimum” type are established for the K₂SO₄, NaBr, KBr solutions. The efficiency of influence of trace impurities on phase equilibria sharply rises in the areas of the temperature‐concentration oscillations (the saturation temperature ranges up to 10 K). The impurity efficiency is promoted by the presence of the amides in its content (as compared with the sulphates) and an increase in length of the hydrocarbon radical. The phenomenon is absent in case of an addition of ion‐inactive compounds. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Liquid phase epitaxy set‐up designed for in situ X‐ray study of SiGe island growth on (001) Si substrates

In situ X‐ray examination at a synchrotron beamline of the solution growth of self‐assembled SiGe structures on silicon (001) substrates through the backside has been realized by a specific heating equipment and a suitable growth assembly. The furnace allows heating of the growth assembly up to 600 °C. The temperature field and the gas flow in the furnace have been numerically modeled. In this way a meaningful estimate about the power consumption and the thermal gradient across the sample has been reached. Despite its low heat capacity and, thus, fast heating and cooling ability the furnace can be stabilized to ± 0.1 K by a high‐performance temperature controller. The growth assembly has been prepared within three separate stages carried out in conventional slideboat liquid phase epitaxy equipment. Such growth assembly allows carrying out then intended experiments without H₂ as normally used in liquid phase epitaxy in favor of N₂, meeting the demand of minimized risks at beamlines. The equipment ensures an easy handling of the growth assembly. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal and EPR investigations of thallium gallium disulphide single crystal

In this research, the results of the differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) investigations of TlGaS₂ single crystal are presented. Specific heat capacity (C_p) anomalies of layered TlGaS₂ have been obtained by using a new DSC technique for such crystals. Remarkable heat capacity anomalies have been revealed at the temperatures of 137.7 K, 174.5 K and 238.5 K. It is found that the anomalies appear at maximum with a small deviation (by 3‐4%) from the regular values, and C_p discontinuity amounted to approximately 5%. Additionally, EPR spectra of Fe doped TlGaS₂ single crystals have been recorded at various temperatures down to 6 K for different orientations of the applied magnetic field. Transformations of present EPR spectra are not sufficient for the confirmation of structural phase transitions, in contrast to the cases in iso structural TlInS₂ and TlGaSe₂ compounds. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transmission electron microscopy investigation of B27 martensitic phase in polycrystalline YCu intermetallic compound

Polycrystalline YCu specimens with a CsCl‐type B2 structure made by induction melting were investigated by transmission electron microscopy (TEM). TEM studies show that an orthorhombic YCu B27 martensite with FeB‐type structure having lattice parameters a = 0.71 nm, b = 0.45 nm and c = 0.54 nm forms during deformation at ambient temperature. (101) twins are observed in the YCu B27 phase. The orientation relationship of B27 with B2 matrix is (001)[1 0]_B27 ‖ (112)[1 0]_B2. Effects of B27 phase formation on the ductility of YCu alloy are discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of nanostructured ZrTiO4 by solid state reaction in equimolar mixture of TiO2 and ZrO2

A solid state reaction in an equimolar mixture of TiO₂ and ZrO₂ was achieved by high‐energy ball‐milling. The ball‐milling first induced the transformation of anatase TiO₂ to high‐pressure phase TiO₂ (II). Nanosized ZrTiO₄ phase was formed from TiO₂(II)/ZrO₂ solid solution by prolonging milling. The finishing of the solid state reaction towards ZrTiO₄ ceramic is investigated in situ at high temperature (< 1100°C) by RS. Reaction is completed at a temperature much lower than reported in literature (1400 – 1600°C). (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)