Entropy increase in the amorphous-to-crystalline phase transition in zirconium tungstate

It has been shown that zirconium tungstate (ZrW₂O₈) exhibits isotropic negative thermal expansion and undergoes pressure-induced amorphization above 1.5 GPa, at room temperature. Now, we have found that amorphous ZrW₂O₈ undergoes endothermic recrystallization, and thus have an overall entropy lower than that of the crystalline phase. This counterintuitive behavior can be rationalized owing to the same low-energy modes already shown to be responsible for the isotropic negative thermal expansion and the anomalously high heat capacity at low temperatures exhibited by ZrW₂O₈. Our findings point to an entire class of materials that should behave similarly to ZrW₂O₈ and constitute direct experimental evidence for an overall entropy increase in an amorphous-to-crystalline transition.     

Use of langmuir probes for monitoring of precursor concentrations during plasma activated chemical vapor deposition of hard coatings

Langmuir-probe characteristics were measured during the deposition of hard zirconium nitride films in H₂ plasmas with tetrakis(diethylamido)-zirconium-Zr[N(C₂H₅)₂]₄- as a precursor. A combination of fast repeatable probe sweeps and hysteresis measurements indicated undisturbed characteristics for approximately 1 h. Since the electron concentration is highly dependent on the partial pressure of the precursor it is possible to use probes as sensors to monitor precursor concentration in a discharge.     

Humidity effect on electrical properties of layered α-zirconium phosphate

The electrical properties of alkali ions exchanged zirconium hydrogen phosphate Zr(HPO₄)₂·H₂O (α-ZrP) are investigated by impedance spectroscopy technique. Cole-cole plots are used to describe the characteristic changes of electrical properties with relative humidity. The evaluated bulk resistance from the equivalent circuit shows exponential dependence of relative humidity. The surface protons of layered (α-ZrP) contribute to electrical conduction. The largest sensitivity is obtained for K ion exchanged systems.     

Protactinium Extraction from Mixed Mineral Acid Solutions. Separation Methods for Pa,Nb, and Zr

Protactinium is highly extracted by tetraphenylarsonium chloride from hydrochloric acid solutions, but niobium and zirconium are extracted as well. The three elements have rather low extractabilities from hydrobromic acid solutions and sulfuric acid solutions. In mixtures of (HCl + H₂SO₄) or (HBr + H₂SO₄), protactinium indicates high distribution coefficients, while niobium and zirconium have again rather low or negligible extractabilities. Results were discussed and data were used to suggest selective conditions for the separation of the three elements.     

Shear viscosity of superfluid He-A1 at low temperatures

The shear viscosity tensor of the A₁-phase of superfluid ³He is calculated at low temperatures and melting pressure, by using the Boltzmann equation approach. The two normal and superfluid components take part in elements of the shear viscosity tensor differently. The interaction between normal and Bogoliubov quasiparticles in the collision integrals is considered in the binary, decay, and coalescence processes. We show that the elements of the shear viscosities η_xy, η_xz, and η_zz are proportional to (T/T_c)⁻². The constant of proportionality is in nearly good agreement with the experimental results of Roobol et al.     

Passivation of defect states in Si-based and GaAs structures

Formation of defect states on semiconductor surfaces, at its interfaces with thin films and in semiconductor volumes is usually predetermined by such parameters as semiconductor growth process, surface treatment procedures, passivation, thin film growth kinetics, etc. This paper presents relation between processes leading to formation of defect states and their passivation in Si and GaAs related semiconductors and structures. Special focus is on oxidation kinetics of yttrium stabilized zirconium/SiO₂/Si and Sm/GaAs structures. Plasma anodic oxidation of yttrium stabilized zirconium based structures reduced size of polycrystalline silicon blocks localised at thin film/Si interface. Samarium deposited before oxidation on GaAs surface led to elimination of EL2 and/or ELO defects in MOS structures. Consequently, results of successful passivation of deep traps of interface region by CN⁻ atomic group using HCN solutions on oxynitride/Si and double oxide layer/Si structures are presented and discussed. By our knowledge, we are presenting for the first time the utilization of X-ray reflectivity method for determination of both density of SiO₂ based multilayer structure and corresponding roughnesses (interfaces and surfaces), respectively.     

Tin(IV) derivatives of 2,6-pyridinedicarboxylate: A Sn Mössbauer spectroscopic investigation

A series of organotin(IV) derivatives of 2,6-pyridinedicarboxylate has been investigated by Mössbauer spectroscopy in order to elucidate aspects concerning bonding and structural features in the solid state. A geometrical pattern of five-fold coordination at the metal centre has been revealed for SnCl₃Bu and SnClBu₃ derivatives. Trans stereochemistry for the butyl and vinyl groups of SnCl₂Bu₂ and SnCl₂(Vin)₂ derivatives has also been identified by this method. The isomer shift for the divinyl derivative is concurrent to a 7-coordinate metal centre contrasting to that for the dibutyl one. Although there is a discrepancy in isomer shift between these compounds, both have seven-fold coordination at the Sn(IV) nucleus. The resulting data has given evidence that 2,6-pyridinedicarboxylate is acting as a tridentate ligand through pyridil and carbolxylate moiety to all derivatives except for SnClBu₃. For the latter, the coordination mode occurs via carboxylate groups. The overall data support distorted geometrical pattern to all complexes in solid state.     

Growth of lithium silicate crystals inside porous silicon film and their exploitation for ozone detection

Silicon dioxide was formed by oxidizing porous silicon film and annealed, in a next step, at 920 °C with lithium nitrate embedded in its structure. These operations have produced the two lithium silicates, Li₂Si₂O₅ and Li₂SiO₃, as it has been confirmed by the X-ray diffraction measurements. At relative high temperature (230 °C), the experimental ionic conductivity of this achieved sample has doubled in presence of ozone flow. A comparison with other samples, prepared with varieties of metallic nitrates and by following the same experimental procedures as for the former one, has proved that the sample prepared with zirconium was also good for ozone detection.     

Unusual thermal conductivity of the negative thermal expansion material, ZrW2O8

In order to investigate the relationship between negative thermal expansion and other thermal properties, the thermal conductivity of the α-phase of ZrW₂O₈ has been determined from 1.9 to 390 K. In addition, the heat capacity was measured from 1.9 to 300 K. The thermal conductivity of ZrW₂O₈ is low, glass-like and close to its theoretical minimum value. The phonon-phonon coupling of the highly anharmonic low-frequency modes which are responsible for negative thermal expansion in ZrW₂O₈ appears to be highly efficient, leading to short phonon mean free paths and exceptionally low thermal conductivity.     

The carrier contribution to the elastic constants in III-V, ternary and quaternary materials in the presence of light waves: Simplified theory, relative comparison and a suggestion for experimental determination

In this paper, we have studied the electronic contribution to the elastic constants for III-V, ternary and quaternary materials in the presence of light waves on the basis of newly formulated electron statistics. It has been found taking n-InAs, n-InSb, n-Hg_1−xCd_xTe and n-In_1−xGa_xAs_yP_1−y lattice matched to InP, as examples that the elastic constants increase with increasing electron concentration, intensity and wavelength in various manners. The strong dependence of the elastic constants on both the light intensity and wavelength reflects the direct signature of the light waves which is in contrast as compared with the corresponding bulk specimens in the absence of photo-excitation. The well-known results for degenerate wide gap materials in the absence of light waves have been obtained as a special case under certain limiting conditions and this compatibility is the indirect test of our generalized formalism. In this context, we have suggested the experimental method of determining the carrier contribution to the elastic constants for materials having arbitrary carrier energy spectra and our results find six important applications in the regime of photon-assisted transport in modern optoelectronic devices.     

Anomalies in low-temperature lattice parameters of ErFeO3 and ErAlO3 single crystals: correlation with magnetic properties

The paper presents the results of an experimental study of thermal expansion of isostructural orthorhombic ErFeO₃ and ErAlO₃ single crystals. Changes of lattice parameters have been investigated by X-ray measurements in the 10-300 K temperature range. Above ∼150 K, experimental results correspond well to the phonon mechanism. At low temperatures distinct anisotropic anomalies were observed in both compounds; and a correlation with the magnetic properties of the relevant ions is noted.     

Formation of hafnium carbide thin films by plasma enhanced chemical vapor deposition from bis(η-cyclopentadienyl)dimethylhafnium as precursor

Thin films of hafnium carbide have been deposited by plasma-enhanced chemical vapor deposition using bis(-cyclopentadienyl)dimethylhafnium, Cp₂ Hf(CH₃)₂, as precursor in 13.56 MHz planar reactor. The influence of the various experimental parameters on film properties has been studied. The carbon content ranged from 11 to 40 weight % and increased with the deposition rate. The film hardness varied between 1300 and 2000 HK. Depending on the carbon content and power delivered in the discharge, the film resistivity and film density ranged from 271 to 10⁵ ·cm and from 3.4 to 10.4 g/cm³, respectively, and the film composition varied from HfC to hafnium containing a-C: H films.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).     

The effect of Gd-doping on the charge ordering state of Bi0.3−xGdxCa0.7MnO3 (0≤x≤0.30)

The effect of Gd-doping on the charge ordering (CO) state in perovskite-type manganates Bi_0.3−xGd_xCa_0.7MnO₃ with x=0, 0.02, 0.05, 0.1, 0.3 has been investigated by transport and magnetic property measurements. It is found that CO temperature (T_CO) and antiferromagnetic (AFM) ordering temperature T_N occurring below T_CO decrease obviously with increasing Gd-doping level. Accompanying the variation of T_CO, the increased magnetization and the decreased resistivity are observed. In addition, the increased magnetic inhomogeneity has been also observed in the samples based on the difference between the zero-field-cooling (ZFC) magnetization M_ZFC and field-cooling (FC) magnetization M_FC, which is ascribed to the competition between ferromagnetic (FM) phase induced by Gd-doping and CO AFM phase. The experimental results indicate that the Bi³⁺ lone pair electron with 6s² character plays a dominating role on the CO state of Bi_0.3Ca_0.7MnO₃.     

Microstructure and interfacial properties of HfO2-Al2O3 nanolaminate films

High-k HfO₂-Al₂O₃ composite gate dielectric thin films on Si(1 0 0) have been deposited by means of magnetron sputtering. The microstructure and interfacial characteristics of the HfO₂-Al₂O₃ films have been investigated by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and spectroscopic ellipsometry (SE). Analysis by XRD has confirmed that an amorphous structure of the HfO₂-Al₂O₃ composite films is maintained up to an annealing temperature of 800 °C, which is much higher than that of pure HfO₂ thin films. FTIR characterization indicates that the growth of the interfacial SiO₂ layer is effectively suppressed when the annealing temperature is as low as 800 °C, which is also confirmed by spectroscopy ellipsometry measurement. These results clearly show that the crystallization temperature of the nanolaminate HfO₂-Al₂O₃ composite films has been increased compared to pure HfO₂ films. Al₂O₃ as a passivation barrier for HfO₂ high-k dielectrics prevents oxygen diffusion and the interfacial layer growth effectively.     

Transmission electron microscopy of Co2(Cr1−xFex)Al sputtered films and their magnetic tunneling junctions

The microstructures of Co₂FeAl and Co₂(Cr_0.4Fe_0.6)Al sputtered films and of their magnetic tunnel junctions (MTJs) have been investigated to discuss the possible reasons for an unexpectedly low tunneling magnetoresistance (TMR). The structure of the Co₂FeAl film changed from B2 to L2₁ with increasing substrate temperature, while that of the Co₂(Cr_0.4Fe_0.6)Al film remained B2 up to 500 °C. The thermodynamically predicted phase separation was not observed in the films. The low TMR values obtained from the MTJs using the Co₂FeAl and Co₂(Cr_0.4Fe_0.6)Al films are attributed to the low-spin polarization expected from the low degree of order in these films. The TMR values depend sensitively on the interfacial structure of the tunnel junctions when the degree of order of the film is low.     

Study on the mechanisms of photoinduced carriers separation and recombination for Fe-TiO2 photocatalysts

The iron(III)-ion doped TiO₂ (Fe³⁺-TiO₂) with different doping Fe³⁺ content were prepared via a sol-gel method. The as-prepared Fe³⁺-TiO₂ nanoparticles were investigated by means of surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), and the photoelectrochemical properties of Fe³⁺-TiO₂ catalysts with different Fe³⁺ content are performed by electrical impedance spectroscopy (EIS) as well as photocatalytic degradation of RhB are studied under illuminating. Based on the experiment results, the mechanism of photoinduced carriers separation and recombination of Fe³⁺-TiO₂ was revealed: that is, the Fe³⁺ captures the photoinduced electrons, inhibiting the recombination of photoinduced electron-hole pairs, this favors to the photocatalytic reaction at low doping concentration (Fe/Ti ≤ 0.03 mol%); while Fe³⁺ dopant content exceeds 0.03 mol%, Fe₂O₃ became the recombination centers of photoinduced electrons and holes because of that the interaction of Fe₂O₃ with TiO₂ leads to that the photoinduced electrons and holes of TiO₂ transfer to Fe₂O₃ and recombine quickly, which is unfavorable to the photocatalytic reaction.     

Breakdown of an intermediate plateau in the magnetization process of anisotropic spin-1 Heisenberg dimer: Theory vs. experiment

The magnetization process of the spin-1 Heisenberg dimer model with the uniaxial or biaxial single-ion anisotropy is particularly investigated in connection with recent experimental high-field measurements performed on the single-crystal sample of the homodinuclear nickel(II) compound [Ni₂(Medpt)₂(μ-ox)(H₂O)₂](ClO₄)₂·2H₂O (Medpt=methyl-bis(3-aminopropyl)amine). The results obtained from the exact numerical diagonalization indicate a striking magnetization process with a marked spatial dependence on the applied magnetic field for arbitrary but finite single-ion anisotropy. It is demonstrated that the field range, which corresponds to an intermediate magnetization plateau emerging at a half of the saturation magnetization, basically depends on a single-ion anisotropy strength as well as a spatial orientation of the applied field. The breakdown of the intermediate magnetization plateau is discussed at length in relation to the single-ion anisotropy strength.     

Dielectric and pyroelectric properties of Langmuir-Blodgett film capacitors

Thin-film parallel-plate capacitors have been prepared by means of the Langmuir-Blodgett (LB) technique with mono- and multilayers of 10,12-pentacosadiynoic acid (polymerized) or arachidic acid as the dielectric [Al(Al₂O₃)-LB-Al structures]. Capacitance, dielectric losses and pyroelectric properties were determined as functions of temperature and number of layers. In spite of the organization of identical molecules in alternating orientation, the overall structure of the LB films was non-centrosymmetric. Pyroelectric coefficients of about 10^–6 C m^–2 K^–1 were derived.     

Analysis of low temperature specific heat in Nd0.5Sr0.5MnO3 and R0.5Ca0.5MnO3 (R=Nd,Sm, Dy and Ho) compounds

We report on the specific heat C(T) of doped manganites Nd_0.5Sr_0.5MnO₃, Nd_0.5Ca_0.5MnO₃, Sm_0.5Ca_0.5MnO₃, Dy_0.5Ca_0.5MnO₃ and Ho_0.5Ca_0.5MnO₃ in the temperature range 2?T?300 K using modified rigid ion model (MRIM). The present specific heat results are in general satisfactory agreement with experimental data except at very low temperatures (i.e. T?12 K). Also a sharp peak observed in the experimental results for these compounds around 5 K could not be revealed by our computed results as they arise due to Schottky-like anomaly. Besides, we have reported the cohesive and the thermal properties of these compounds. The results obtained by us are discussed in detail.