Electrical transport properties of Fe3−xCrxO4 ferrite films on MgO (0 0 1) grown by molecular beam epitaxy

In this report, we fabricated a series of Fe_3−xCr_xO₄(0≦x≦2) films by plasma-oxygen-assisted molecular beam epitaxy (MBE) and did structural and electrical characterizations of these films. These films show textured single phase quality and the lattice parameters are consistent with those of the bulk at low Cr composition (x<0.9). However, the lattice parameters show severe deviation from the bulk value in the intermediate region of 0.9≦x≦1.5 and no diffraction can be resolved at x∼2. These discrepancies may be attributed to the cation distributions and the instability of spinal structure as Cr concentration becomes dominant. The resistivity presents a typical Arrhenius temperature dependence with ρ=ρ₀ exp (E_p/k_BT) indicating that the transport is due to a hopping mechanism. The prefactor ρ₀ increases in Fe_3−xCr_xO₄, at smaller x but tends to level out for x>1, suggesting that Cr³⁺ ions may start to replace Fe³⁺ ions at the A site in the high x region. The activation energy of electrical hopping gradually increases at low Cr concentration but abruptly rises to ∼110 meV at x>0.9, suggesting a crossover from electron-hopping mediated transport to a thermally activated band gap excitation.     

Oxygen-induced p(3 × 1) reconstruction of the W(1 0 0) surface

The oxidation of the W(1 0 0) surface at elevated temperatures has been studied using room temperature STM and LEED. High exposure of the clean surface to O₂ at 1500 K followed by flash-annealing to 2300 K in UHV results in the formation of a novel p(3 × 1) reconstruction, which is imaged by STM as a missing-row structure on the surface. Upon further annealing in UHV, this surface develops a floreted LEED pattern characteristic of twinned microdomains of monoclinic WO_x, while maintaining the p(3 × 1) missing-row structure. Atomically resolved STM images of this surface show a complex domain structure with single and double W〈0 1 0〉 rows coexisting on the surface in different domains.     

X-ray photoelectron spectroscopy characterization of the layered intercalated compound K2xMn1 − xPS3

Polycrystalline powders of the layered MnPS₃ compound have been intercalated with K⁺ ions by ion-exchange to yield the K_2xMn_1 − xPS₃ intercalate. X-ray photoelectron spectroscopy has been applied to learn about the electronic structure of this compound. In particular, we have studied the XPS spectra of the Mn 2p and 3p, P and S 2p, K 2p and 3p core levels and of the valence band region. The binding energies for various core levels of the elements present in this compound and their observed chemical shifts are analyzed. The data give evidence for the lack of non-equivalent atoms of K, Mn, P and S. Shake-up satellites are present at the Mn 2p and 3p core levels. The occurrence of such lines allows us to hypothesize that K_2xMn_1 − xPS₃ is a large-gap insulating Mn compound. Confirmation that only an ion transfer accompanies the intercalation process is given from both the strong observed similarity with the corresponding XPS spectra in MnPS₃ and the observed binding energy positions of the K 2p and 3p levels. As regards the valence band XPS spectrum, the observed analogies with the corresponding XPS spectra of the pure compound and of other K compounds have allowed us to single out two regions and their probable contributors.     

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).     

Charge order melting and magnetic transition in Nd0.5(1+x)Ca0.5(1−x)Mn(1−x)CrxO3 system

The magnetic property of double doped manganite Nd_0.5(1+x)Ca_0.5(1−x)Mn_(1−x)Cr_xO₃ with a fixed ratio of Mn³⁺:Mn⁴⁺=1:1 has been investigated. For the undoped sample, it undergoes one transition from charge disordering to charge ordering (CO) associated with paramagnetic (PM)-antiferromagnetic (AFM) phase transition at T<250 K. The long range AFM ordering seems to form at 35 K, rather than previously reported 150 K. At low temperature, an asymmetrical M-H hysteresis loop occurs due to weak AFM coupling. For the doped samples, the substitution of Cr³⁺ for Mn³⁺ ions causes the increase of magnetization and the rise of T_c. As the Cr³⁺ concentration increases, the CO domain gradually becomes smaller and the CO melting process emerges. At low temperature, the FM superexchange interaction between Mn³⁺ and Cr³⁺ ions causes a magnetic upturn, namely, the second FM phase transition.     

Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi₁₄W_1 − xLa_xO_{24 − 3x/2} (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi₂O₃ related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi₂O₃ type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ₈₀₀ = 1.34 S cm^− 1), but also shows significant phase separation at lower temperatures.     

Anisotropy and FOMP in Tb3 (Fe28−xCox) V1.0 (x=0, 3 and 6) compounds

In this work, the structural and magnetic properties of Tb₃ (Fe_28−xCo_x) V_1.0 (x=0, 3, 6) compounds have been investigated. The structural characterization of compounds by X-ray powder diffraction is an evidence for a monoclinic Nd₃(Fe, Ti)₂₉-type structure (A2/m space group). The refined lattice parameters a and b (but not c) and the unit cell volume V, obtained from the XRD data by the Rietveld method, are found to decrease with increasing Co concentration. The unit cell parameters behavior has been attributed to the smaller Co atoms and a preferential substitution of Fe by Co. The anisotropy field (H_a) as well as critical field (H_cr) was measured using the singular point detection (SPD) technique from 5 to 300 K in a pulsed magnetic field of up to 30 T. At T=5 K, a FOMP of type 2 was observed for all samples and persists at all temperatures up to 300 K. For sample x=0, H_cr=10.6 and 2.0 T at 5 and 300 K, respectively, is equal to that reported earlier. The occurrence of canting angles between the magnetic sublattices during the magnetization process instead of high-order anisotropy contributions (at room temperature are usually negligible) has been considered to explain the survival of the FOMP at room temperature. The anisotropy and critical fields behave differently for samples with x=0, 3 compared with x=6. The observed behavior has been related to the fact that the Co substitution for Fe takes place with a preferential entrance in the inequivalent crystallographic sites of the 3:29 structure. The contribution of the Tb-sublattice in the Tb₃(Fe, V)₂₉ compound with uniaxial anisotropy has been scaled from the anisotropy field measured on a Y₃(Fe, V)₂₉ single crystal with easy plane anisotropy.     

Effect of a LaSrCoO3 buffer layer on Pb1 − xLaxTi1 − x/4O3 films studied by polarized Raman spectroscopy

A confocal Raman investigation of Pb_1 − xLa_xTi_1 − x/4O₃ (PLT) thin films grown by RF magnetron sputtering on PbO_x/Pt/Ti/SiO₂/Si substrates with an intermediate LaSrCoO₃ (LSCO) layer was performed. The influence of the LaSrCoO₃ buffer layer was analyzed taking advantage of the observed Raman spectral band variation, which varied according to different manufacturing procedures. In the presence of a LSCO layer, the A1(1TO) Raman mode, which was indicative of tetragonal distortion, was pronouncedly enhanced, and a slight deviation from the (0 0 1) plane of the film was observed from the angular dependence of the polarized Raman spectral intensity. Furthermore, the spectral band variation as well as the residual stress along the in-depth direction was measured in the film from cross-sectional spectral line scans. This latter measurement showed a relaxation of the lattice mismatch in the presence of LSCO and PbO layers.     

High-temperature electrical properties of magnesiowustite Mg1 − xFexO and spinel Fe3 − x − yMgxCryO4 ceramics

Phase relationships, thermal expansion and electrical properties of Mg_1 − xFe_xO (x = 0.1-0.45) cubic solid solutions and Fe_{3 − x − y}Mg_xCr_yO_4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O₂)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10^− 6 K^− 1 at 300-500 K and (13.2-16.1) × 10^− 6 K^− 1 at 1050-1370 K. Mg_1 − xFe_xO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.     

Global SO(3) × SO(3) × U(1) symmetry of the Hubbard model on bipartite lattices

In this paper the global symmetry of the Hubbard model on a bipartite lattice is found to be larger than SO(4). The model is one of the most studied many-particle quantum problems, yet except in one dimension it has no exact solution, so that there remain many open questions about its properties. Symmetry plays an important role in physics and often can be used to extract useful information on unsolved non-perturbative quantum problems. Specifically, here it is found that for on-site interaction U ≠ 0 the local SU(2) × SU(2) × U(1) gauge symmetry of the Hubbard model on a bipartite lattice with N_a^D sites and vanishing transfer integral t = 0 can be lifted to a global [SU(2) × SU(2) × U(1)]/Z₂² = SO(3) × SO(3) × U(1) symmetry in the presence of the kinetic-energy hopping term of the Hamiltonian with t > 0. (Examples of a bipartite lattice are the D-dimensional cubic lattices of lattice constant a and edge length L = N_aa for which D = 1, 2, 3,... in the number N_a^D of sites.) The generator of the new found hidden independent charge global U(1) symmetry, which is not related to the ordinary U(1) gauge subgroup of electromagnetism, is one half the rotated-electron number of singly occupied sites operator. Although addition of chemical-potential and magnetic-field operator terms to the model Hamiltonian lowers its symmetry, such terms commute with it. Therefore, its 4^N_aD energy eigenstates refer to representations of the new found global [SU(2) × SU(2) × U(1)]/Z₂² = SO(3) × SO(3) × U(1) symmetry. Consistently, we find that for the Hubbard model on a bipartite lattice the number of independent representations of the group SO(3) × SO(3) × U(1) equals the Hilbert-space dimension 4^N_aD. It is confirmed elsewhere that the new found symmetry has important physical consequences.     

Magnetic characterization of Bi(Fe1 − xMnx)O3

Bi(Fe_1 − xMn_x)O₃ ceramics (x up to 0.3) were prepared by rapid sintering. Weak ferromagnetism with two magnetic anomalies at low temperatures was observed for Bi(Fe_0.95Mn_0.05)O₃ and Bi(Fe_0.9Mn_0.1)O₃. From temperature-dependent magnetic relaxation measurements, the anomalies at 20 K and 100 K are related to the freezing of cluster spin glass.     

Anomalous behavior of ultrasonic properties near 50 K in Rb0.30MoO3 and Rb0.30(Mo1−xVx)O3

Depending on the temperature, the charge density wave (CDW) nonlinear conductivity of the blue bronzes A_0.30MoO₃ (A=K, Rb) shows two different regimes: a strongly damped motion above ∼50 K and motion with almost no damping below ∼50 K. In a search for an elastic signature of this CDW behaviour, we performed ultrasonic measurements on Rb_0.30MoO₃ and Rb_0.30(Mo_1−xV_x)O₃ single crystals between 4 K and 300 K. In Rb_0.30MoO₃, at T∼50 K, upon cooling, a large increase of the sound velocity is observed. The ultrasonic attenuation coefficient shows an increase down to 50 K followed by a plateau. In Rb_0.30(Mo_1−xV_x)O₃ (x=0.4 at%) the anomaly broadens and is shifted towards higher temperatures. The results are discussed in terms of CDW glass.     

Depth-dependent fct to fcc strain relaxation in CoxNi1−x/Cu3Au(1 0 0) alloy films

Co_xNi_1−x/Cu₃Au(1 0 0) with x ? 11% was prepared at room temperature to study the strain relaxation and their correlation with the spin-reorientation transition. The vertical interlayer distance relaxed from 1.66 Å (fct) to 1.76 Å (fcc) while the thickness increased from 8 ML to 18 ML. Such rapid strain relaxation with thickness was attributed to the larger lattice mismatch between Co_xNi_1−x and Cu₃Au(1 0 0) (η ∼ −6.5%). The smooth change for crystalline structure was observed during strain relaxation process in which the crystalline structure seems irrespective of the alloy composition. To explain the strain relaxation, a phenomenological model was proposed. We provide a physical picture that the deeper layers may not relax while the surface layer start to relax. This assumption is based on the several experimental studies. Using the strain averaged from all layers of thin film as the volume strain of magneto-elastic anisotropy energy, the interrelation between strain relaxation and spin reorientation transition can be well described in a Néel type magneto-elastic model.     

RAIRS studies of CO adsorption on Pd/CeO2−x(1 1 1)/Pt(1 1 1)

Reflection absorption infrared spectroscopy (RAIRS) has been used to investigate the adsorption of CO on CeO_2−x-supported Pd nanoparticles at room temperature. The results show that when CeO_2−x is initially grown on Pt(1 1 1), a small proportion of the surface remains as bare Pt sites. However, when Pd is deposited onto CeO_2−x/Pt(1 1 1), most of the Pd grows directly on top of the CeO_2−x(1 1 1). RAIR spectra of CO adsorption on 1 ML Pd/CeO_2−x/Pt(1 1 1) show a broad CO-Pd band, which is inconsistent with a single crystal Pd surface. However, the 5 ML and 10 ML Pd/CeO_2−x/Pt(1 1 1) spectra show vibrational bands consistent with the presence of Pd(1 1 1) and (1 0 0) faces, suggesting the growth of Pd nanostructures with well defined facets.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

A variable temperature EPR study of the manganites (La1/3Sm2/3)2/3SrxBa0.33−xMnO3 (x=0.0, 0.1, 0.2, 0.33): Small polaron hopping conductivity and Griffiths phase

Four manganite samples of the series, (La_1/3Sm_2/3)_2/3Sr_xBa_0.33−xMnO₃, with x=0.0, 0.1, 0.2 and 0.33, were investigated by X-band (∼9.5 GHz) electron paramagnetic resonance (EPR) in the temperature range 4-300 K. The temperature dependences of EPR lines and linewidths of the samples with x=0.0, 0.1 and 0.2, containing Ba²⁺ ions, exhibit similar behavior, all characterized by the transition temperatures (T_C) to ferromagnetic states in the 110-150 K range. However, the sample with x=0.33 (containing no Ba²⁺ ions) is characterized by a much higher T_C=205 K. This is due to significant structural changes effected by the substitution of Ba²⁺ ions by Sr²⁺ ions. There is an evidence of exchange narrowing of EPR lines near T_min, where the linewidth exhibits the minimum. Further, a correlation between the temperature dependence of the EPR linewidth and conductivity is observed in all samples, ascribed to the influence of small-polaron hopping conductivity in the paramagnetic state. The peak-to-peak EPR linewidth was fitted to ΔB_pp(T)=ΔB_pp,min+A/Texp(−E_a/k_BT), with E_a=0.09 eV for x=0.0, 0.1 and 0.2 and E_a=0.25 eV for x=0.33. From the published resistivity data, fitted here to σ(T)∝1/T exp(−E_σ/k_BT), the value of E_σ, the activation energy, was found to be E_σ=0.18 eV for samples with x=0.0, 0.1 and 0.2 and E_σ=0.25 eV for the sample with x=0.33. The differences in the values of E_a and E_σ in the samples with x= 0.0, 0.1and 0.2 and x=0.33 has been ascribed to the differences in the flip-flop and spin-hopping rates. The presence of Griffiths phase for the samples with x=0.1 and 0.2 is indicated; it is characterized by coexistence of ferromagnetic nanostructures (ferrons) and paramagnetic phase, attributed to electronic phase separation.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Conduction mechanism and the dielectric relaxation process of a-Se75Te25−xGax (x=0, 5, 10 and 15 at wt%) chalcogenide glasses

Se₇₅Te_25−xGa_x (x=0, 5, 10 and 15 at wt%) chalcogenide compositions were prepared by the well known melt quenching technique. Thin films with different thicknesses in the range (185–630 nm) of the obtained compositions were deposited by thermal evaporation technique. X-ray diffraction patterns indicate that the amorphous nature of the obtained films. The ac conductivity and the dielectric properties of the studied films have been investigated in the frequency range (10²–10⁵ Hz) and in the temperature range (293–333 K). The ac conductivity was found to obey the power low ω^s where s≤1 independent of film thickness. The temperature dependence of both ac conductivity and the exponent s can be well interpreted by the correlated barrier hopping (CBH) model. The experimental results of the dielectric constant ε₁ and dielectric loss ε₂ are frequency and temperature dependent. The maximum barrier height W_m calculated from the results of the dielectric loss according to the Guintini equation, and agrees with that proposed by the theory of hopping of charge carriers over a potential barrier as suggested by Elliott for chalcogenide glasses. The density of localized state was estimated for the studied film compositions. The variation of the studied properties with Ga content was also investigated. The correlation between the ac conduction and the dielectric properties were verified.     

Spectral line parameters in the (3 ← 0) overtone band of the HI molecule and line-mixing in the band head

The linestrengths, self-pressure broadening and shifting coefficients have been measured for P₃ (10)- R₃ (12) lines in the second overtone band of hydrogen iodide. A dipole moment function in terms of the reduced nuclear displacement x = (R − R_e)/R_e is obtained using rotationless dipole matrix elements determined by the Herman-Wallis analysis of the (1, 2, 3 ← 0) HI bands: μ (x) = 0.4471(5) − 0.0770(2)x + 0.547(3)x² − 1.93(2)x³, in a full agreement with the function proposed previously [J. Mol. Spectrosc. 223 (2004) 67]. A close match is demonstrated of the results of most recent relativistic calculations [Phys. Chem. Chem. Phys. 6 (2004) 3779] with the spectroscopically derived electric dipole parameters for HI. Line-mixing in the band head is observed, the self-pressure shifting and broadening coefficients for the (3 ← 0) band lines are determined.