Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Studies of divacancy in Si using positron lifetime measurement

The charge state dependence of positron lifetime and trapping at divacancy (V₂) in Si doped with phosphorus or boron has been studied after 15 McV electron irradiation up to a fluence of 8.0×10¹⁷ e/cm². The positron trapping cross sections for V ₂ ^2– , V ₂ ^– and V ₂ ⁰ at 300 K were about 6×10^–14, 3×10^–14 and 0.1–3×10^–14 cm², respectively. For V ₂ ⁺ , however, no positron trapping was observed. The marked difference in the cross sections comes from Coulomb interaction between the positron and the charged divacancy. The trapping rates for V ₂ ⁰ and V ₂ ^2– have been found to increase with decreasing temperature in the temperature range of 10–300 K. These results are well interpreted by a two-stage trapping model having shallow levels with energy of 9 meV (V ₂ ⁰ ) and 21 meV (V ₂ ^2– ). The appearance of a shallow level for V ₂ ⁰ can not be explained by a conventional Rydberg state model. The lifetime (290–300 ps) in V ₂ ⁰ is nearly constant in the temperature range from 10 to 300 K, while that in V ₂ ^2– increases from 260 ps at 10 K to 320 ps at 300 K. The lifetime (260 ps) in V ₂ ^2– is shorter than that in V ₂ ⁰ at low temperature, which is due to the excess electron density in V ₂ ^2– . At high temperature, however, the longer lifetime of V ₂ ^2– than that of V ₂ ⁰ is attributed to lattice relaxation around V ₂ ^2– .     

Photoinduced Oxidation of Diphenylbisanthene and Its Spectral Manifestations

The absorption and fluorescence spectra of diphenylbisanthene (DPB) in n-octane and benzene at 300 and 77 K have been investigated. The appreciable Stokes shift of the fluorescence band (180 cm^–1 in n-octane and 440 cm^–1 in benzene) points to the nonplanar character of the aromatic skeleton of DPB, which has been confirmed by results of the optimization of the molecule geometry by the AMI quantum-mechanical method. It has been found that spectral manifestations of the products of photoinduced transformations of DPB molecules are observed in the UV region (200–350 nm), and it has been shown that the observed photochemical process is two orders of magnitude less effective than for diphenylhelianthrene. On the basis of the experimental data and the results of the quantum-chemical calculations of the electronic spectra of molecules of DPB and endoperoxides (ZINDO/S method), it has been concluded that the end products of DPB phototransformations are its endobiperoxides in which —O—O— groups are added to the phenyl-substituted benzene rings of the aromatic skeleton.     

Anion dependence of the valence state detrapping behavior for a fused hydrocarbon bridged binuclear mixed valence iron compound and its di-oxygen sensitivity

Monocationic forms of the symmetric and asymmetric indacene bridged species [(Cp^*Fe)₂(-s-indacene)],I, and [(Cp^*Fe)₂(-as-indacene)],II, are fully detrapped and trapped, respectively, over the entire range from 1.5 K to ambient temperature as their BF ₄ ^– salts. In contrast to [II ⁺][BF ₄ ^– ], the TCNE^.– salt [II ⁺][TCNE^.–] exhibits a transition from fully trapped to a largely detrapped valence state behaviour over the increasing temperature range 100 to 300 K. Mössbauer spectra ofI suggest that while it is relatively insensitive to oxygen as a neat solid, it is strongly oxidized by O₂ in dry hexane solution. Similar studies ofII indicate essential insensitivity to O₂, both as a solid and in hexane solution.     

The effect of temperature on the electrical characteristics of Ti/n-GaAs Schottky diodes

Schottky diodes still attract researchers as they are used in various device applications. This study provides I–V characteristics of Ti/n-GaAs (80–300 K). Higher barrier height (Φ_B0) values were obtained for higher temperatures, whereas the ideality factor exhibited the opposite behavior. This was associated with a barrier inhomogeneity at the Ti/GaAs interface, which has a Gaussian distribution (GD). The mean barrier height values calculated from the modified Richardson and Φ_B0 - q/2 kT plots were found to be 0.584 eV and 0.575 eV in the temperature range of 80–160 K. They were found as 1.041 eV and 1.033 eV between 180 K and 300 K, respectively. The modified Richardson constant value, on the other hand, was calculated as 22.06 A cm⁻² K⁻² (80–160 K) and 13.167 A cm⁻² K⁻² (180–300 K). These values are higher than the theoretical value for n-GaAs, which is 8.16 A cm⁻² K⁻². This difference may stem from intense inhomogeneity at the Ti/n-GaAs interface.     

N2-, O2-, and air-broadened half-widths, their temperature dependence, and line shifts for the rotation band of H2O

Complex Robert–Bonamy (CRB) calculations of the half-width, its temperature dependence, and the line shift have been made for the rotation band transitions of H₂¹⁶O for N₂ or O₂, as the bath molecule. First the atom–atom component of the intermolecular potential was adjusted to reproduce the half-widths of the 22 and 183 GHz transition determined by Payne et al. (IEEE Trans. Geosci. Remote Sensing 46 (2007) 3601–3617). Then the line shape parameters were determined at seven temperatures (200, 225, 275, 296, 350, 500, and 700 K) for the H₂O–N₂ and H₂O–O₂ systems. The air-broadened values were determined at each temperature by the standard method. The half-widths, their temperature dependence, and the line shifts were studied as a function of the rotational quantum numbers. Estimating line shape parameters by scaling from one perturbing gas to another was investigated. The calculations were compared with measurement.     

Apparent conflicting indications on the conformation of dimethylether–argon from the rotational spectra of the d6 and C species

The rotational spectra of dimethylether–d₆–Ar and dimethylether–¹³C–Ar have been investigated by molecular beam Fourier transform microwave spectroscopy. The obtained rotational constants, when compared to those of the normal species, give contrasting indications on the conformation of the complex. We believe the indications given by the dimethylether–Ar/dimethylether–¹³C–Ar pair to be the correct ones. They suggest the Ar atom to lie in the σ_ν symmetry plane of dimethylether perpendicular to the C–O–C plane, shifted towards the oxygen atom. This conformation is in agreement with several kinds of theoretical calculations. Probably isotopic substitution effects make the data from dimethylether–d₆–Ar not directly compatible with those of the other species.     

Structural and magnetic studies of Fe2O3/SiO2 granular nanocomposites

Fe₂O₃/SiO₂ nanocomposites were synthesized by mechanical alloying, using Fe and SiO₂ powders as precursors. After 340 h milling, the sample essentially consists of hematite and amorphous silica. TEM images show hematite particles embedded in and surrounded by an amorphous silica matrix. A broad size distribution—5–50 nm—of hematite particles is found, and other group of very small—2–3 nm—unidentified particles are observed. Room temperature Mössbauer spectra show a paramagnetic doublet, which may correspond to a non-crystalline phase in the sample (probably the small unidentified particles), and a sextet corresponding to hematite. Magnetic properties were investigated by measuring hysteresis curves at different temperatures (5–300 K) and by zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves (10 mT). The hysteresis loops were well fitted by a ferromagnetic contribution. No evidence of Morin transition is found down to 5 K.     

Correlation between P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18·3H2O and Li6P6O18

To understand the surprising behavior between the variations of the P′–P–P″ angles and the correlated variations of the O′–P–O″ ones, two lithium cyclohexaphosphate compounds Li₆P₆O₁₈·3H₂O and Li₆P₆O₁₈ are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P₆O₁₈]⁶⁻ ring anions but with 3m or internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of ⁷Li and ³¹P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for ⁷Li or ³¹P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the ³¹P chemical shift tensor is dependent on the deviations of the O–P–O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P′–P–P″ and the ones of the O′–P–O″ is related to the overall charge on the PO₄ group. We also find the positions of the isotropic lines for ⁷Li essentially depend on the site co-ordination of this nuclei.     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.     

Optical measurements of the superconducting gap in MgB 2

Far-infrared reflectivity studies on the polycrystalline intermetallic compound MgB₂ with a superconducting transition temperature T _c = 39 K were performed at temperatures 20 K to 300 K. We observe a significant raise of the superconducting-to-normal state reflectivity ratio below 70 cm ^-1 , with a maximum at about 25-30 cm ^-1 , which gives a lower estimate of the superconducting gap of 2Δ(0) ≈ 3-4 meV. Received 7 March 2001 and Received in final form 18 April 2001     

Molecular dynamics simulation comparison of atomic scale intermixing at the amorphous Al2O3/semiconductor interface for a-Al2O3/Ge, a-Al2O3/InGaAs, and a-Al2O3/InAlAs/InGaAs

The structural properties of a-Al₂O₃/Ge, a-Al₂O₃/In_0.5Ga_0.5As and a-Al₂O₃/In_0.5Al_0.5As/InGaAs interfaces were investigated by density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic a-Al₂O₃ samples were generated using a hybrid classical-DFT MD “melt and quench” approach. The interfaces were formed by annealing at 700 K/800 K and 1100 K with subsequent cooling and relaxation. The a-Al₂O₃/Ge interface demonstrates pronounced interface intermixing and interface bonding exclusively through Al–O–Ge bonds generating high interface polarity. In contrast, the a-Al₂O₃/InGaAs interface has no intermixing, Al–As and O–In/Ga bonding, low interface polarity due to nearly compensating interface dipoles, and low substrate deformation. The a-Al₂O₃/InAlAs interface demonstrated mild intermixing with some substrate Al atoms being adsorbed into the oxide, mixed Al–As/O and O–Al/In bonding, medium interface polarity, and medium substrate deformation. The simulated results demonstrate strong correlation to experimental measurements and illustrate the role of weak bonding in generating an unpinned interface for metal oxide/semiconductor interfaces.     

Absorption Spectra of Single Crystals of EuGa2S4 and EuGa2S4:Co

The optical properties of EuGa₂S₄ and EuGa₂S₄:Co single crystals in a range of temperatures from 77 to 300 K are investigated. The single crystals are obtained by the Bridgman method and are characterized by tetragonal syngony. The behavior of the optical transitions in the photon energy range 1.70–2.45 eV and the temperature range 77–300 K is determined. It is established that in the energy range 1.77–1.90 eV absorption is associated with transitions of the Co²⁺ ion, while in the range 2.20–2.40 eV, with indirect allowed optical transitions.     

PAC studies of AgIn2 andAg2In growth kinetics at the Ag-In interface

The formation of AgIn₂ andAg₂In compounds at Ag-In interface in Ag/In electrodeposited samples was studied by TDPAC in an isothermal annealing experiment in annealing temperatures 300–423 K. For 300 K the AgIn₂ average thickness growth was found to follow a square root of time dependence but for higher temperatures a saturation like effect was observed. At annealing temperature 423 K the Ag₂In formation took place anda linear growth of its average thickness versus t^1/2 was found.     

Crystallographic and magnetic structures of highT c related (Bi/Pb)2Sr2FeO6.25 determined by neutron powder diffraction

The structure of (Bi/Pb)₂Sr₂FeO_6.25 was refined from high resolution neutron powder diffraction data taken at 300 K and 5 K. The average structure is well described in the orthorhombic spacegroup Amaa witha=5.4254 Å,b=5.4909 Å andc=23.2245 Å. The FeO₆ octahedra are tilted by 2.7° towards (0 1 0). The oxygen positions in the (Bi/Pb)O-layers are consistent with the occurrence of (Bi/Pb)–O–(Bi/Pb) chains. Excess oxygen was located between these chains. Antiferromagnetic 3-dim ordering of the Fe-moments withM=(2, 1, 2) _B was observed at 5 K with the wavevector pointing along (1 0 0).     

Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

Valence fluctuations and oxygen dimerization in high-temperature superconductors from X-ray photoemission spectroscopy

The high-temperature superconducting Cu oxides — which are intrinsically Mott insulators — are strongly correlated metals because of valence fluctuations involving Cud ⁹–d ¹⁰ configurations. Temperature-dependent X-ray photoemission spectroscopy of theO 1s and Cu 2p levels in the range 10–300 K provides evidence for O-dimerization, with corresponding increase of the Cud ¹⁰O 2p ⁵ well-screened XPS-final state belowT _c . This supports the suggestion of dynamical mixed-valence and double-exchange antiferromagnetic interaction as an important mechanism for the origin of highT _c superconductivity.     

Conformational Analysis of Baclofen Analogues by 1H and 13C NMR: Phaclofen,Saclofen, and Hydroxy-Saclofen. Influence of the Anionic Moiety

The conformations of three analogues of baclofen 1: phaclofen, saclofen, and hydroxy-saclofen 2–4, potent GABA_B antagonists, in solution (D₂O) are estimated from high-resolution (300 MHz) H NMR coupling data. Conformations and populations of conformers are calculated by means of a modified Karplus-like relationship for the vicinal coupling constants. H NMR spectral analysis evidences how 1–3 keep in solution the preferred a conformation around C3-C4 bond. A partial rotation is set up around C2–C3 bond (the conformations about C2–C3 are all highly populated in solution) particularly for 2 and 3 while 1 shows a relative preferred a conformation. This evidences the influence of the anionic moiety.     

High resolution study of anion formation in low-energy electron attachment to SF<Subscript>6</Subscript> molecules in a seeded supersonic beam

Using two variants of the Laser Photoelectron Attachment (LPA) method involving a differentially-pumped, seeded supersonic beam (0.05% and 12.5% of SF₆ molecules in helium carrier gas, nozzle temperatures T₀= 300–600 K, stagnation pressures p₀= 1–5 bar) and mass spectrometric ion detection, we have investigated the energy dependence of anion formation in low-energy electron collisions with SF₆ molecules at high energy resolution. Using the standard LPA method, the yield for SF₆^- as well as SF₅^- and F^- anions was studied with an energy width around 1 meV over the electron energy range 0–200 meV. In addition, a variant of the LPA method with extended energy range (denoted as EXLPA) was developed and applied to measure the yield for SF₆^- and SF₅^- formation over the energy range 0–1.5 eV with an energy width of about 20 meV. The cross-section for formation of SF₆^- decreases by five orders of magnitude over the range 1–500 meV and is only weakly dependent on nozzle temperature. The yield for SF₅^- formation shows — apart from a weak zero energy peak which grows strongly with rising temperature — a broad maximum (located around 0.6 eV for T₀= 300 K and shifting to lower energies with rising T₀) and a monotonical decrease towards higher energies. SF₅^- attachment spectra taken at elevated temperatures exhibit changes with rising stagnation pressure which directly reflect rovibrational cooling of the SF₆ molecules with rising pressure. The SF₅^-/SF₆^- intensity ratio at near-zero energy and the low-energy shape of the broad peak in the SF₅^- spectra are used as thermometers for the internal temperature of the SF₆ molecules in the seeded supersonic beam which (at p₀= 1 bar) are found to be 50–100 K lower than the nozzle temperature. The energy dependence of the yield for F^- formation is similar to that for SF₆^-, but the F^- signals are three to four orders of magnitude lower than those for SF₆^-; in view of the rather high endothermicity of F^- formation the origin of the F^- signals is discussed in some detail.     

Phase transitions in [Ni(NH3)6](NO3)2

Electric permittivity ^* = ′ − i″ of nickel-hexammino nitrate (NHN) has been measured within the range of temperature from 9 to 300 K at a frequency of 8.8 GHz (X-band). It has been found that the phase transitions at T_k1 = 247 K and T_k2 = 90 K are discontinuous structural transitions between centrosymmetric phases, whereas the transition at T_c = 63 K is a continuous phase transition (glass?).