Nanoscale anglesite growth on the celestite (0 0 1) face

In situ atomic force microscopy (AFM) was used to study the growth behaviour of anglesite (PbSO₄) monolayers on the celestite (0 0 1) face. Growth was promoted by exposing the celestite cleavage surfaces to aqueous solutions that were supersaturated with respect to anglesite. The solution supersaturation, β_ang, was varied from 1.05 to 3.09 (where β_ang = a(Pb²⁺) · a(SO₄²⁻)/K_sp,ang). In this range of supersaturation, two single anglesite monolayers (3.5 Å in height each) from pre-existent celestite steps were grown. However, for solution supersaturation β_ang < 1.89 ± 0.06, subsequent multilayer growth is strongly inhibited. AFM observations indicate that the inhibition of a continuous layer-by-layer growth of anglesite on the celestite (0 0 1) face is due to the in-plane strain generated by the slight difference between the anglesite and celestite lattice parameters (i.e. the linear misfits are lower than 1.1%). The minimum supersaturation required to overcome the energy barrier for multilayer growth gave an estimate of the in-plane strain energy: 11.4 ± 0.6 mJ/m²_. Once this energy barrier is overcome, a multilayer Frank–Van Der Merwe epitaxial growth was observed.     

Water incorporation into the Ba2(In1 − xMx)2O5‪ (M = Sc 0 ≤ x < 0.5 and M = Y 0 ≤ x < 0.35) system and protonic conduction

Ba₂(In_1 − xM_x)₂O_{5 − y / 2}(OH)_y‪□_{1 − y / 2} (y ≤ 2; M = Sc³⁺ 0 ≤ x < 0.5 and M = Y³⁺ 0 ≤ x < 0.35) compounds were prepared by reacting Ba₂(In_1 − xM_x)₂O₅‪ phases with water vapor. This reaction is reversible. Analyses of the hydration process by TG and XRD studies show that the thermal stability of hydrated phases increases when x increases and that the incorporation of water is not a single-phase reaction inducing either a crystal system or space group modification. Fully hydrated (y = 2) and dehydrated (y = 0) samples have been stabilized at room temperature and characterized for all compositions. In wet air, all phases show a proton contribution to the total conductivity at temperatures between 350 and 600 °C. At a given temperature, proton conductivity increases with the substitution ratio and reaches at 350 °C, 5.4 10^− 3 S cm^− 1 for Ba₂(In_0.65Sc_0.35)₂O_4.2□_0.2(OH)_1.6.     

Optical investigation of ferromagnetic Ga1−xMnxN layers grown on sapphire (0 0 0 1) substrates

We have investigated the temperature-dependent photoluminescence (PL) spectra in Ga_1−xMn_xN layers (where x≈0.1–0.8%) grown on sapphire (0 0 0 1) substrates using the plasma-enhanced molecular beam epitaxy technique. All the layers doped with manganese exhibited n-type conductivity with Curie temperature over 350 K. The efficient PL are peaked in the red (1.86 eV), yellow (2.34 eV), and blue (3.29 eV) spectral range. It was found that the blue band at 3.29 eV is mostly associated with the formation complexes between donors (e.g., N vacancy) and Mn acceptors, which results in forming donor levels at 0.23 eV below the conduction band edge. The yellow band is attributed to intrinsic gallium defects. The broad band at 1.86 eV is attributed to inner ⁵D state transition (T₂ to E) of Mn ions.     

Defect chemical and statistical thermodynamic studies on oxygen nonstoichiometric Nd2 − xSrxNiO4 + δ

In order to elucidate how oxygen content changes in Nd_2 − xSr_xNiO_4 + δ (x = 0, 0.2, 0.4), defect chemical and statistical thermodynamic analyses were carried out. The relationship among δ, P(O₂), and T were analyzed by a defect equilibrium model. Since Nd_2 − xSr_xNiO_4 + δ shows metal like band conduction at high temperatures, chemical potential of hole is expressed by the integration of the Fermi-Dirac distribution function and the density of state. The nonstoichiometric variation of oxygen content in Nd_2 − xSr_xNiO_4 + δ can be explained by the defect equilibrium model with a regular solution approximation. Partial molar entropy and partial molar enthalpy of oxygen are calculated from the nonstoichiometric data and Gibbs–Helmholtz equation. The relationship among defect structure, defect equilibrium, and thermodynamic quantities is elucidated by the statistical thermodynamic model. Thermodynamic quantities are calculated by the statistical thermodynamic model with the results of defect chemical analysis and compared with those obtained from experimental results. Thermodynamic quantities calculated by the statistical thermodynamic model can explain rough tendency of those obtained from the δ–T–P(O₂) relationship.     

Density functional study of the adsorption of aspirin on the hydroxylated (0 0 1) -quartz surface

In this study the adsorption geometry of aspirin molecule on a hydroxylated (0 0 1) α-quartz surface has been investigated using DFT calculations. The optimized adsorption geometry indicates that both, adsorbed molecule and substrate are strongly deformed. Strong hydrogen bonding between aspirin and surface hydroxyls, leads to the breaking of the original hydroxyl–hydroxyl hydrogen bonds (Hydrogenbridges) on the surface. In this case new hydrogen bonds on the hydroxylated (0 0 1) α-quartz surface appear which significantly differ from those at the clean surface. The 1.11 eV adsorption energy reveals that the interaction of aspirin with α-quartz is an exothermic chemical interaction.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Annealing effect on the superconductivity of In2O3–ZnO thin films

We have investigated the relation among ρ–T characteristics, superconductivity, annealing conditions and the crystallinity of polycrystalline (In₂O₃)_1−x–(ZnO)_x films. We annealed as-grown amorphous films in air by changing annealing temperature and time. It is found that the films annealed at 200 °C or 300 °C for a time over 0.5 h shows the superconductivity. Transition temperature T_c and the carrier density n are T_c < 3.3 K and n ≈ 10²⁵–10²⁶ m⁻³, respectively. Investigations for films with x = 0.01 annealed at 200 °C have revealed that the T_c, n and crystallinity depend systematically on annealing time. Further, we consider that there is a suitable annealing time for sharp resistive transition because the transition width becomes wider with longer annealing times. We studied the upper critical magnetic field H_c2(T) for the film with different annealing time. From the slope of dH_c2/dT for all films, we have obtained the resistivity ρ dependence of the coherence length ξ(0) at T = 0 K.     

Oxygen vacancy-induced aging of Mn-doped Ba0.8Sr0.2TiO3 ceramics in paraelectric and ferroelectric state

The aging properties of 0.01 mol% Mn-doped Ba_0.8Sr_0.2TiO₃ ceramics have been investigated from 30 °C to 400 °C at various frequencies. Decreases in ε′(T) of the aged sample compared to the fresh one around the tetragonal–cubic transition and in the regime of diffusion have been observed. The activation energy E_a = 1.25 eV obtained from the J–T loop at zero electric field indicates that oxygen vacancies dominate in the aging. The symmetry-conforming principle of point defects was employed to explain the time and temperature dependence of aging in the dielectric constant and double/constricted P–E loops of the samples aged in the paraelectric and ferroelectric state.     

Ab initio study of the chemical states of water on Cr2O3(0 0 0 1): From the isolated molecule to saturation coverage

The reactivity of the (0 0 0 1)-Cr–Cr₂O₃ surface towards water was studied by means of periodic DFT + U. Several water coverages were studied, from 1.2H₂O/nm² to 14.1H₂O/nm², corresponding to ¼, 1, 2 and 3 water/Cr at the (0 0 0 1)-Cr₂O₃ surface, respectively. With increasing coverage, water gradually completes the coordination sphere of the surface Cr atoms from 3 (dry surface) to 4 (1.2 and 4.7H₂O/nm²), 5 (9.4H₂O/nm²) and 6 (14.1H₂O/nm²). For all studied coverages, water replaces an O atom from the missing above plane. At coverages 1.2 and 4.7H₂O/nm², the Cr–O_s (surface oxygen) acid–base character and bond directionality govern the water adsorption. The adsorption is molecular at the lowest coverage. At 4.7H₂O/nm², molecular and dissociative states are isoenergetic. The activation energy barrier between the two states being as low as 12 kJ/mol, allowing protons exchanges between the OH groups, as evidenced by ab inito molecular dynamics at room temperature. At coverages of 9.4 and 14.1H₂O/nm², 1D- (respectively, 2D-) water networks are formed. The resulting surface terminations are –Cr(OH)₂ and –Cr(OH)₃– like, respectively. The increased stability of those terminations as compared to the previous ones are due to the stabilization of the adsorbed phase through a H-bond network and to the increase in the Cr coordination number, stabilizing the Cr (t_2g) orbitals in the valence band. An atomistic thermodynamic approach allows us to specify the temperature and water pressure domains of prevalence for each surface termination. It is found that the –Cr(OH)₃-like, –Cr(OH)₂ and anhydrous surfaces may be stabilized depending on (T, P) conditions. Calculated energies of adsorption and OH frequencies are in good agreement with published experimental data and support the full hydroxylation model, where the Cr achieves a 6-fold coordination, at saturation.     

Electrical characteristics and low-temperature sintering of BiFeO3-modified Pb(Zr,Ti)O3–Pb(Fe2/3W1/3)O3–Pb(Mn1/3Nb2/3)O3 ceramics with ZnO addition

Effects of ZnO addition on electrical properties and low-temperature sintering of BiFeO₃-modified Pb(Zr,Ti)O₃–Pb(Fe_2/3W_1/3)O₃–Pb(Mn_1/3Nb_2/3)O₃ were investigated. The investigations revealed that the sintering temperature can be decreased to 950 °C, and the favorable properties were obtained with 0.10 wt% ZnO added ceramics. The electrical properties were as follows: d₃₃ = 313 pC/N, K_p = 0.56, tan δ = 0.0053, ε_r = 1407 and T_c = 295 °C, which showed that this system was a promising material for the multilayer devices application.     

Friction between α-Al2O3(0 0 0 1) surfaces and the effects of surface hydroxylation

Molecular dynamics simulations were performed to study the friction between hydroxylated α-Al₂O₃(0 0 0 1) surfaces at the temperature of 300 K. Effects of the degree of surface hydroxylation and sliding velocity have been discussed. Results indicate that the friction coefficient decreases with increased degrees of hydroxylation. For all degrees of surface hydroxylation, the friction law crosses over from thermal activation to viscous damping at sliding velocity of 80 m/s.     

Observation of the π(1800) and (1880) mesons in decay

A partial-wave analysis of the reaction π⁻p→ηηπ⁻p at 18 GeV/c has been performed on a data sample of approximately 4000 events obtained by Brookhaven experiment E852. The J^PC=0⁻⁺π(1800) state is observed in the a₀(980)η and f₀(1500)π decay modes. It has a mass of 1876±18±16 MeV/c² and a width of 221±26±38 MeV/c². The J^PC=2⁻⁺π₂(1880) meson is observed decaying through a₂(1320)η. It has a mass of 1929±24±18 MeV/c² and a width of 323±87±43 MeV/c². Both states are potential candidates for non-exotic hybrid mesons.     

Solubility and acid-base properties and activity coefficients of chitosan in different ionic media and at different ionic strengths, at T = 25 °C

Studies on the acid-base properties and solubility of a polyammonium polyelectrolyte (chitosan) with different molecular weights (MW 310 and 50 kDa), were performed at T = 25 °C, in the pH range 2.5–7. The protonation of chitosan was investigated by potentiometry ([H⁺]-glass electrode) in NaCl, NaNO₃ and mixed NaNO₃ + Na₂SO₄ ionic media, at different ionic strengths. Protonation constants were calculated as a function of dissociation degree α by means of two different models, namely, a simple linear model and the modified Henderson–Hasselbalch equation. Experimental data were also fitted using a model independent of α (Diprotic-like model), according to which the acid-base properties can be simply described by two protonation constants in all the acidic pH range. The dependence on ionic strength of protonation constants in NaCl aqueous solution was modelled by Specific ion Interaction Theory (SIT). The ion pair formation between protonated chitosan and Cl⁻, NO₃⁻ and SO₄²⁻ was also considered, and the relative formation constants are reported.Solubility investigations were performed in NaCl aqueous solutions in a wide range of ionic strength (0.1 < I/mol L^− 1 < 3.0), with the aim to determine the activity coefficients of neutral species and the Setschenow coefficient of chitosan 310 kDa.     

Atomic and electronic properties of furan on the Si(0 0 1)-(2 × 2) surface

The atomic and electronic properties of the adsorption of furan (C₄H₄O) molecule on the Si(1 0 0)-(2 × 2) surface have been studied using ab initio calculations based on pseudopotential and density functional theory. We have considered two possible chemisorption mechanisms: (i) [4 + 2] and (ii) [2 + 2] cycloaddition reactions. We have found that the [4 + 2] interaction mechanism was energetically more favorable than the [2 + 2] mechanism, by about 0.2 eV/molecule. The average angle between the CC double bond and Si(1 0 0) surface normal was found to be 22°, which is somewhat smaller than the experimental value of 28°, but somewhat bigger than other theoretical value of 19°. The electronic band structure, chemical bonds, and theoretical scanning tunneling microscopy images have also been calculated. We have determined a total of six surface states (one unoccupied and five occupied) in the fundamental band gap. Our results are seen to be in good agreement with the recent near edge X-ray absorption fine structure and high resolution photoemission spectroscopy data.     

Oxide ion conductivity and relaxation in CaREZrNbO7 (RE = La, Nd, Sm, Gd, and Y) system

CaREZrNbO₇ (RE = La, Nd, Sm, Gd and Y) system changed from fluorite (F)-type to pyrochlore (P)-type structure when the ionic radius ratios, r(Ca²⁺–RE³⁺)_av/r(Zr⁴⁺–Nb⁵⁺)_av were larger than 1.34. Thus, the La, Nd, and Sm compounds have a cubic P-type structure and the Gd and Y ones have a defect F-type structure. The electrical conductivity was measured using complex-plane impedance analysis over a wide temperature (300–750 °C) and frequency (1 Hz–1 MHz) ranges. The conductivity relaxation phenomenon was observed in these compounds and the relaxation frequencies were found to show Arrhenius-type behavior and activation energies were in good agreement with those obtained from high temperature conductivity plots. These results support the idea that the relaxation process and the conductivity have the same origin. The ionic conductivity of CaREZrNbO₇ (RE = La, Nd, Sm, Gd and Y) system showed the maximum at the phase boundary between the F-type and P-type phases. On the other hand, the activation energy for the conduction decreased in the F-type phase and increased in the P-type phase with increasing ionic radius ratio. Among the prepared compounds, CaGdZrNbO₇ showed the highest ionic conductivity of 9.47 × 10^− 3 S/cm at 750 °C which was about twice as high as that observed in Gd₂Zr₂O₇ (4.2 × 10^− 3 S/cm at 800 °C). The grain morphology observation by scanning electron microscope (SEM) showed well-sintered grains. AC impedance measurements in various atmospheres further indicated that they are predominantly oxide ion conductors at elevated temperatures (> 700 °C).     

Li mobility in Li0.5 − xNaxLa0.5TiO3 perovskites (0 ≤ x ≤ 0.5): Influence of structural and compositional parameters

The dependence of Li mobility on structure and composition of Li_0.5 − xNa_xLa_0.5TiO₃ perovskites (0 ≤ x ≤  0.5) has been investigated by means of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. At 300 K, all samples display a rhombohedral superstructure (R-3c S.G.), where octahedra are out of phase tilted along [111] direction of the ideal cubic cell. The elimination of the octahedral tilting is responsible for the rhombohedral–cubic transformation, detected near 1000 K. In these perovskites, La and Na cations are randomly distributed in A sites, but Li ions are fourfold coordinated at unit cell faces of the cubic perovskite. Lithium conductivity, σ_300 K, decreases with the sodium content, decreasing from values typical of fast ionic conductors, 10^− 3 S/cm, to those of good insulators, 10^− 10 S/cm, when the interconnectivity between vacant A sites is lost (x > 0.3). In samples with x < 0.3, dc conductivity displays a non-Arrhenius behaviour, decreasing activation energy from ~ 0.37 to 0.25 eV when the sample is heated between 77 and 500 K. The temperature dependence of B_Li factors shows the existence of two regimes for Li motion. Below 373 K, Li ions remain partially located near square oxygen windows that connect contiguous A sites, but above 400 K, extended Li motions become dominant. The additional decrease of activation energy from 0.25 to 0.16 eV (low-temperature ⁷Li NMR value), should require the full elimination of octahedral tilting which is only produced above 1000 °C.     

Free radical reactions at the Ru(0 0 0 1) surface: Atomic oxygen and dissociated NH3

X-ray photoelectron spectroscopy was used to study the effect of atomic oxygen on Ru(0 0 0 1), and the effect of dissociated ammonia on RuO₂/Ru(0 0 0 1), in UHV conditions at ambient temperature. The Ru(0 0 0 1) surface was exposed, at ambient temperature, to a mixed flux of atomic and molecular oxygen generated by dissociation of O₂ in a thermal catalytic cracker, with 45% dissociation efficiency. The detailed study of the XPS spectra shows the formation of a disordered multilayer oxide (RuO₂). No formation of higher oxides of Ru was observed. The formation of RuO₂ proceeded without saturation for total oxygen exposures of up to 10⁵ Langmuir, at which point an average oxide thickness of 68 Å was observed. RuO₂ formed by the reaction with atomic oxygen was exposed to a flux of NH_x (x = 1, 2) + H generated by the cracker. The reduction of RuO₂ to Ru metal was observed by XPS. An exposure of 3.6 × 10² L of NH_x + H, resulted in the observation of adsorbed H₂O and OH, but no evidence of lattice oxide. The chemisorbed species were removed by additional NH_x + H exposure. No nitrogen adsorption was observed.     

The effect of defects on the hydrogenation in Mg (0 0 0 1) surface

Density-functional theory was presented to investigate the hydrogen dissociation on a pure, Pt-doped, vacancy and oxide Mg(0 0 0 1) surface. Our results show that the energy barriers are 1.05, 0.39, 0.93 and 1.33 eV for H₂ dissociation on the pure, Pt-doped, vacancy and oxide Mg surface, respectively. The calculation results imply that the initial dissociation of H₂ is enhanced significantly for the Pt-doped Mg(0 0 0 1) surface, negligible for the vacancy model and weekend for the oxide model. The density of state results shows that, following the dissociation reaction coordinate, the H–H interactions are weeker for the Pt-doped model while interactions become stronger for the oxide model. It is suggested that the dissociation process is facilitated when Pt atom acts as catalyst and oxide overlayers delay hydrogen adsorption on the Mg layer. The present study will help us understand the defect role being played for the improvement or opposition effect in absorption kinetics of H₂ on the Mg(0 0 0 1) surface.     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.     

Thermal annealing effects on I–V–T characteristics of sputtered Cr/n-GaAs diodes

Sputtered Cr/n-GaAs Schottky diodes have been prepared and annealed at 200 and 400 °C. The current–voltage (I–V) characteristics of the as-deposited and annealed diodes have been measured in the temperature range of 60–320 K with steps of 20 K. The effect of thermal annealing on the temperature-dependent I–V characteristics of the diodes has been investigated experimentally. The ideality factor and barrier height (BH) values for 400 °C annealed diode approximately remain unchanged from 120 to 320 K, and those of the as-deposited sample from 160 to 320 K. The departures from ideality at low temperatures have been ascribed to the lateral fluctuations of the BH. The BH values of 0.61 and 0.74 eV for the as-deposited and 400 °C annealed diodes were obtained at room temperature, respectively. A Richardson constant value of 9.83 A cm⁻² K⁻² for 400 °C annealed Schottky diode, which is in close agreement with the known value of 8.16 A cm⁻² K⁻² for n-type GaAs. Furthermore, T₀ anomaly values of 15.52, 10.68 and 5.35 for the as-deposited and 200 and 400 °C annealed diodes were obtained from the nT versus T plots. Thus, it has been seen that the interface structure and quality improve by the thermal annealing at 400 °C.