Reversibility window in as-quenched Ge-As-S glasses

Thermoanalytical characteristics and Raman scattering of high purity sulfur and ternary bulk glasses Ge_xAs_xS_(100−2x) for x=4-22 at. % were studied. The intermediate phase characterized by vanishing of non-reversing heat flow ΔH_nr, i.e. so-called the thermally reversing window was found between mean coordination number 〈r〉∼2.28-2.47. Separated phase of non-crystalline cycloocta-S, manifesting itself by λ-transition at ∼155 °C, was found for glasses with sulfur content higher than ∼80 at.%. Raman spectra of studied Ge-As-S glasses showed different shapes in three different areas according to three distinct phases of network glasses-floppy, intermediate, rigid.     

Ferromagnetic nature of (Ga, Cr)As epilayers revealed by magnetic circular dichroism

A systematic study of magnetic circular dichroism (MCD) was carried out in a wave length range 500-960 nm for (Ga_1−x, Cr_x)As epilayers with x=2.38% and 4.59% grown by the low temperature molecular beam epitaxy (LT-MBE) technique. Hysteresis characteristics showed up indeed in the magnetic field dependence of both MCD and magnetization measured by the superconductor quantum interference device (SQUID). The Curie temperature of the (Ga_1−x, Cr_x)As epilayer was determined to be about 12 K by the Arrott approach. The present result provides evidences that there is strong coupling of the Cr spins to the GaAs host band structure in (Ga_1−x, Cr_x)As samples. That affects the critical point of the semiconductor host, and makes the magnetization behavior in a plot of M∼B/T (magnetic field divided by temperature) substantially different from standard superparamagnetism.     

Investigation of the solid solution series 2(MnX)-CuInX2 (X=S, Se)

(2MnX)_x(CuInX₂)_1−x with X=S and Se were prepared by solid state reaction from the end members α-MnS, β-MnS and CuInS₂ in the range 0<x≤0.2 (≤0.6 for β-MnS) as well as MnSe and CuInSe₂ in the range 0<x≤0.1. Mixed crystals with 0≤x≤0.1 crystallize in the tetragonal chalcopyrite type structure, (2α-MnS)_x(CuInS₂)_1−x samples with 0.1<x≤0.2 and (2β-MnS)_x(CuInS₂)_1−x samples up to x=0.6 consist of two phases, occuring as tetragonal domains (x∼0.1 for X=S) within a cubic matrix with zinc-blende type structure (x∼0.4 for X=S), indicating a miscibility gap. For tetragonal single phase samples the band gap energy, the lattice constants and the anion parameter have been determined. The first and the latter ones show a different composition dependent behaviour caused by the modification of the MnS (α-MnS with NaCl type structure, β-MnS with zinc-blende type structure) used during the synthesis. Additionally a CuMn_xIn_1−xS₂ powder sample, in which Mn substitutes the M^III site, was investigated. The SQUID measurements revealed a well-distinct magnetic transition between 15 and 16 K as well as ferromagnetic-like hysteresis loops pronounced for temperatures below the transition temperature. Below this temperature a clear splitting between the zero field cooling (ZFC) and the field cooling (FC) curves indicate to the existence of a long-range magnetic ordering phenomenon. This behaviour was not found in the other samples were Mn substitutes both sites M^I as well as M^III.     

Piezoelectric properties of [Li0.03(K0.48Na0.52)0.97](Nb0.97Sb0.03)O3-(Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 lead-free piezoelectric ceramics

[Li_0.03(K_0.48Na_0.52)_0.97](Nb_0.97Sb_0.03)O₃-(Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ [(1−x)LKNNS-xBCTZ] lead-free piezoelectric ceramics were prepared by the conventional solid state method, and effects of BCTZ content on the piezoelectric properties of LKNNS ceramics were mainly investigated. A stable solid solution has been formed between LKNNS and BCTZ, and a morphotropic phase boundary of (1−x)LKNNS-xBCTZ ceramics is identified in the range of 0 < x ≤ 0.02. The Curie temperature of (1−x)LKNNS-xBCTZ ceramics decreases with increasing BCTZ content. A higher ?_r value and a lower tan δ value are demonstrated for the (1−x)LKNNS-xBCTZ ceramic with x = 0.02. The (1−x)LKNNS-xBCTZ ceramic with x = 0.02 has an enhanced electrical behavior of d₃₃ ∼ 237 pC/N, k_p ∼ 48.6%, ?_r ∼ 1451, tan δ ∼ 0.037, and T_c ∼ 335 °C. As a result, (1−x)LKNNS-xBCTZ ceramics are promising candidate materials for the field of lead-free piezoelectric materials.     

Thermoelectric properties and electronic structure of Te-doped CoSb3 compounds

Co₄Sb_12−xTe_x compounds were prepared by mechanical alloying combined with cold isostatic pressing, and the effects of Te doping on the thermoelectric properties were studied. The electronic structure of Te-doped and undoped CoSb₃ compounds has been calculated using the first-principles plane-wave pseudo-potential based on density functional theory. The experimental and calculated results show that the value of the solution limit x of Te in Co₄Sb_12−xTe_x compounds is between 0.5 and 0.7. The Fermi surface of CoSb₃ is located between the conduction band and the valence band, and its electrical resistivity decreases with increasing temperature. The density of states is mainly composed of Co 3d and Sb 5p electrons for intrinsic CoSb₃.The Fermi surface of Te-doped compounds moves to the conduction band and its electrical resistivity increases with increasing temperature, exhibiting n-type degenerated semiconductor character. Under the conditions of the experiment, the maximum value 2.67 mW/m K² of the power factor for Co₄Sb_11.7Te_0.3 is obtained at 600 K; this is about 14 times higher than that of CoSb₃.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Transport properties and non-stoichiometry of La_1−xCa_xW_1/6O₂ and La_1−yW_1/6O₂ (x=0, 0.005, 0.05; y=0.05, 0.1) have been characterized by means of impedance spectroscopy, the EMF-technique, H⁺/D⁺ isotope exchange, and thermogravimetry in the temperature range 300-1200 °C as a function of oxygen partial pressure and water vapor partial pressure. The materials exhibit mixed ionic and electronic conductivities; n- and p-type electronic conduction predominate at high temperatures under reducing and oxidizing conditions, respectively. Protons are the major ionic charge carrier under wet conditions and predominates the conductivity below ∼750 °C. The maximum in proton conductivity is observed for LaW_1/6O₂ with values reaching 3×10⁻³ S/cm at approximately 800 °C. The high proton conductivity for the undoped material is explained by assuming interaction between water vapor and intrinsic (anti-Frenkel) oxygen vacancies.     

Tuning hydrogen storage properties and reactivity: Investigation of the LiBH4-NaAlH4 system

Tuning the hydrogen storage properties of complex metal hydrides is of vast interest. Here, we investigate the hydrogen release and uptake pathways for a reactive hydride composite, LiBH₄−NaAlH₄ utilizing in situ synchrotron radiation powder X-ray diffraction experiments. Sodium alanate transforms to sodium borohydride via a metathesis reaction during ball milling or by heating at T∼95 °C. NaBH₄ decomposes at ∼340 °C in dynamic vacuum, apparently directly to solid amorphous boron and hydrogen and sodium gas and the latter two elements are lost from the sample. Under other conditions, T=400 °C and p(H₂)=∼1 bar, NaBH₄ only partly decomposes to B and NaH. On the other hand, formation of LiAl is facilitated by dynamic vacuum conditions, which gives access to the full hydrogen contents in the LiBH₄−NaAlH₄ system. Formation of AlB₂ is observed (T∼450 °C) and other phases, possibly AlB_x or Al_1−xLi_xB₂, were observed for the more Li-rich samples. This may open new routes to the stabilization of boron in the solid state in the dehydrogenated state, which is a challenging and important issue for hydrogen storage systems based on borohydrides.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

Infrared reflectivity of Cox(SiO2)1−x (x∼0.85, 0.55, 0.38) granular films on SiO2 glass substrates

We report the infrared specular reflectivity of Co_x(SiO₂)_1−x (x∼0.85, 0.55, 0.38) films on SiO₂ glass spanning from a metal-like to insulating behavior. While films for x∼0.85 show carrier metallic shielding and hopping conductivity, for x∼0.65 and lower concentrations, the nanoparticles’ number and size promote a localization edge near the highest longitudinal optical frequency. Such an edge is associated with a reflectivity minimum and a higher frequency band connoting strong electron-phonon interactions, carrier phonon assisted hopping, and polaron formation. Optical conductivity fits with current polaron models provide grounds toward a microscopic understanding of transport properties in these as-prepared granular films.     

Mg substitution in CuCrO2 delafossite compounds

A detailed investigation of the series CuCr_1−xMg_xO₂ (x=0.0-0.05) has been performed by making high-temperature resistivity and thermopower measurements, and by performing a theoretical analysis of the latter. Microstructure characterization has been carried out as well. Upon Mg²⁺ for Cr³⁺ substitution, a concomitant decrease in the electrical resistivity and thermopower values is found, up to x∼0.02-0.03, indicating a low solubility limit of Mg in the structure. This result is corroborated by scanning electron microscopy observations, showing the presence of MgCr₂O₄ spinels as soon as x=0.005. The thermopower is discussed in the temperature-independent correlation function ratio approximation as based on the Kubo formalism, and the dependence of the effective charge carrier density on the nominal Mg substitution rate is addressed. This leads to a solubility limit of 1.1% Mg in the delafossite, confirmed by energy dispersive X-ray spectroscopy analysis.     

Ferroelectricity in antiferromagnetic phases of Eu1−xY xMnO3

This work reports an experimental investigation of the ferroelectric character of magnetic phases of the orthorhombic Eu_1−xY _xMnO₃ system at low temperatures. The temperature dependence of the polarization curves clearly reveals the existence of a re-entrant improper ferroelectric phase for x=0.2, 0.3 and 0.5. A ferroelectric phase is also stable for x=0.4, and we have no experimental evidence for its vanishing down to 7 K. From these and early results obtained using other experimental techniques, the corresponding (x,T) phase diagram was traced, yielding significant differences with regard to the ones previously reported.     

Effect of sulfur additive on density of localized states in nanostructures chalcogenide Se95−xSxZn5 thin films

This paper reports the measurement of space charge limited conduction (SCLC) on the fabricated thin films of Se_95−xS_xZn₅ (0.2≤x≤10) in temperature range 313–353 K for the first time. At high electric fields (E∼10⁴ V/cm), the current could be fitted into the theory of space charge limited conduction, in case of uniform distribution of localized states in mobility gap. The homogeneity and surface morphology of thin films were assessed by scanning electron microscopy. The crystalline nature of the thin films was confirmed by powder XRD and the crystallite size was calculated using Scherer's formula. The crystallite size and density of localized states were found to increase with the increase of sulfur concentration. DC conductivity and activation energy were calculated and found to decrease and increase respectively, with the increase of sulfur concentration.     

Thermal conductivity of silver doped lanthanum manganites between 10 and 300 K

Thermal conductivity (λ) of nanocrystalline La_1−xAg_xMnO₃ (x=0.05, 0.15, 0.25, 0.3) pellets prepared by pyrophoric method is reported between 10 and 300 K. Magnitude of thermal conductivity has been found to be strongly influenced by monovalent (Ag) substitution at the La site. Silver doping in LaMnO₃ enhances T_C of the system to ∼299 K. Qualitative nature of the temperature variation of thermal conductivity of the silver substituted lanthanum manganites remains closely similar to that for divalent doped systems. Our analysis demonstrates that in La_1−xAg_xMnO₃ also, the mechanism of heat conduction is predominantly by phonons. The contribution of the electronic part is only ∼1% of the total λ. The spin wave contribution is also estimated close to T_C, which for all the samples lies within ∼2%. At temperatures below ∼100 K, the measured data have been analyzed using phonon relaxation time method and the strengths of the various phonon scattering processes have been estimated. Our analysis further suggests strong influence of phonon scattering by 2D like defects in the thermal conductivity of monovalent doped lanthanum manganites at low temperatures (<70 K) in the ferromagnetic region.     

Structure and magnetic properties of FexPd1−x thin films

Fe_xPd_1−x films were epitaxially grown on Au(001). The structure changes from face-centered-cubic (fcc) to face-centered-tetragonal (fct) at x∼0.6, then to body-centered-cubic (bcc) at x∼0.85. Ferromagnetism shows up at 300 K when x is 0.06. The cubic magnetocrystalline anisotropy constant K₁ switches from negative to positive as x increases to 0.34.     

Effect of multielement doping on low-field magnetotransport in La0.7−xMmxCa0.3MnO3 (0.0?x?0.45) manganite

We report the synthesis, structure and low-field magnetotransport properties of Mischmetal (Mm)-doped La_0.7−xMm_xCa_0.3MnO₃ (0?x?0.45) manganite. Mischmetal—Mm—is a natural mixture of rare earth elements La, Ce, Pr and Nd with ∼28%, 50%, 6% and 16% composition, respectively. All the samples crystallize in orthorhombic structure. Increasing x (Mm), corresponding to decreasing the La-site average ionic radii (〈r_A〉) hence increasing the size mismatch (i.e. variance σ²), results in strong suppression of ferromagnetism (T_C) and the associated metallicity (T_IM). It may be pointed out that Mm (La, Ce, Pr and Nd) substitution has been done to create two effects. First, creation of multivalence of Mn (2+, 3+ and 4+) via Ce substitution and second to create higher degree of disorder due to size difference brought in not only by Ce but also by Pr and Nd. Evidences and arguments based on XPS analysis suggest that multivalent ions La, Mm and Ca, and the resulting presence of Mn²⁺, Mn³⁺ and Mn⁴⁺, causes the simultaneous operation of ferromagnetism-double exchange (Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺) and antiferromagnetic-superexchange (Mn³⁺/Mn³⁺ and Mn²⁺/Mn²⁺) interaction. In addition, Mm doping also creates inhomogenities at La—as well as Mn—site due to size and valency difference. A curiously huge magnetoresistance as high as ∼63% for x=0.35, under a moderate magnetic field of ∼10 kOe has been observed and even at low magnetic field of ∼3 kOe MR is ∼30%. The competing double exchange and superexchange coupled with inhomogenities are the most likely cause for the occurrence of large ∼63% CMR in the Mm-doped LCMO.     

Electrical and microscopic characterization of ZnO films on p-SiC substrates

ZnO/p- SiC heterojunctions were fabricated by thermal evaporation from ZnO high quality powder (99.99%) onto 4H and 6H p-SiC polytypes. We find that, despite the low cost technique employed for the deposition of the ZnO film, the devices exhibited breakdown voltages in excess of 100 V, high rectification ratio (forward to reverse current ratio, I_F/I_R) and low leakage current, respectively, 2×10⁵ and 4.5×10⁻⁷ A/cm² (for the 4H p-SiC based device) and 5×10⁴ and 5×10⁻⁷ A/cm² (for the 6H p-SiC based device). The current-voltage (I×V) characteristics were also measured at the nanometer scale by means of conductive atomic force microscopy. A simple Schottky diode model and conductance divided by current versus conductance plots (G/I×G plots) was used to analyze device characteristics. This analysis shows that, when probing at the nanometric scale, fluctuations of the effective barrier height and/or surface states across individual grains or grain boundaries cause deviations from linear G/I×G plots. These fluctuations are smeared out when probing at the macroscale and thus it becomes possible to obtain linear plots and extract diode parameters.     

The stable structures of iron pnictides AFeAs (A = alkali and alkaline-earth metals): A first principles study

We have investigated the structural stabilities of iron arsenide compounds A_x(FeAs)_1−x (A = alkali and alkaline-earth metals) by first principles calculations. We find that (i) all of the experimental “122” type structures with composition x=1/3 are stable; (ii) all of the “111” type structures with composition x=1/2 except CsFeAs are stable; (iii) K₃FeAs with composition x=3/4 is stable. The predicted stable KFeAs, RbFeAs, SrFeAs, BaFeAs, K₃FeAs have the As-Fe-As bond angles close to the ideal tetrahedral angles, indicating that they may be superconductors.     

A Hall coefficient investigation of ferromagnetic Ga1−xMnxAs layers on (100) GaAs substrates

Ferromagnetic Ga_1−xMn_xAs epilayers with Mn mole fraction in the range of x≈2.2-4.4% were grown on semi-insulating (100) GaAs substrates using the molecular beam epitaxy technique. The transport properties of these epilayers were investigated through Hall effect measurements. The measured hole concentration of Ga_1−xMn_xAs layers varied from 4.4×10¹⁹ to 3.4×10¹⁹ cm⁻³ in the range of x≈2.2-4.4% at room temperature. From temperature dependent resisitivity data, the sample with x≈4.4% shows typical behavior for insulator Ga_1−xMn_xAs and the samples with x≈2.2 and 3.7% show typical behavior for metallic Ga_1−xMn_xAs. The Hall coefficient for the samples with x≈2.2 and 4.4% was fitted assuming a magnetic susceptibility given by Curie-Weiss law in a paramagnetic region. This model provides good fits to the measured data up to and the Curie temperature T_c was estimated to be 65, 83 K and hole concentration p was estimated to be 5.1×10¹⁹, 4.6×10¹⁹ cm⁻³ for the samples with x≈2.2 and 4.4%, respectively, confirming the existence of an anomalous Hall effect for metallic and insulating samples.     

Meeting experimental challenges to physics of network glasses: Assessing the role of sample homogeneity

We introduce a Raman profiling method to track homogenization of Ge_xSe_100−x melts in real time, and show that 2 g melts reacted at 950 °C in high vacuum homogenize in 168 h on a scale of 10μm. Homogenization of melts is precursive to self-organization of glasses. In the present glasses, compositional variation of Raman active corner-sharing mode frequency of GeSe₄ units, molar volumes, and the enthalpy of relaxation at T_g, reveal the rigidity (x_c(1)=19.5(3)%) and the stress (x_c(2)=26.0(3)%) transitions to be rather sharp (Δx<0.6%). These abrupt elastic phase transitions are in harmony with rigidity theory and have a direct bearing on the physics of glasses.