Raman spectroscopic study of carbon substitution in MgB2

We study the effect of carbon doping on the Raman spectrum of the MgB₂ superconductor. Out data show that significant changes in the Raman spectra of the MgB_2−xC_x compounds occur for carbon concentrations x>0.04. The E_2g mode at ∼580 cm⁻¹ hardens only moderately upon increased doping despite direct carbon substitution in the boron layers, while the dependence of its full width at half maximum (FWHM) on x reveals the competing effects of reduced electron-phonon coupling and increased disorder. The results are discussed in the framework of anisotropic lattice contraction and the position of the σ sub-bands with respect to the Fermi energy level. The relative intensity of the phonon peak at ∼770 cm⁻¹, associated with a peak in the phonon density of states, increases considerably and dominates for x=0.08. Additionally, it hardens and broadens with increasing x in the range 0.04-0.08. These changes can be associated with carbon substitution-induced disorder in the investigated samples.     

Preparation of REFeAsO1−xFx (RE=Sm and Gd) superconductors at a relatively low temperature

A series of the SmFeAsO_1−xF_x and GdFeAsO_1−xF_x (x=0.05, 0.1, 0.15, 0.2, 0.25) samples have been prepared using nano-scaled ReF₃ as the fluorine resource at a relatively low temperature. The samples have been sintered at 1100 and 1120 °C for SmFeAsO_1−xF_x and GdFeAsO_1−xF_x, respectively. These temperatures are at least 50-60° lower than other previous reports. All of the so-prepared samples possess a tetragonal ZrCuSiAs-type structure. Dramatically supression of the lattice parameters and increase in T_c proved that this low temperature process was more effective to introduce fluorine into R_EFeAsO. Superconducting transition appeared at 39.5 K for SmFeAsO_1−xF_x with x=0.05 and at 22 K for GdFeAsO_1−xF_x with x=0.1. The highest T_c was detected to be 54 K in SmFeAsO_0.8F_0.2 and 40.2 K in GdFeAsO_0.75F_0.25. The use of the nano-scaled ReF₃ compounds has improved the efficiency of the present low temperature method in synthesizing the fluorine-doped iron-based superconductors.     

The 2ν1, 2ν2 and 2ν3 overtones of FClO3

The infrared spectra of the 2ν₁, 2ν₂ and 2ν₃ overtones of perchloryl fluoride, FClO₃, have been recorded at high resolution using monoisotopic pure samples. Four symmetric top species have been investigated: F³⁵Cl¹⁶O₃, F³⁷Cl¹⁶O₃, F³⁵Cl¹⁸O₃ and F³⁷Cl¹⁸O₃. The v_i = 2, i = 1, 2, 3 vibrationally excited states are totally symmetric, so these overtones correspond to parallel bands of medium/weak intensity, centered from 2010 to 2120 cm⁻¹ (2ν₁), from 1390 to 1430 cm⁻¹ (2ν₂) and from 1070 to 1100 cm⁻¹ (2ν₃). Most of the bands are unperturbed and their analysis was straightforward. The band origins, the rotational and centrifugal molecular constants in the v₁ = 2, v₂ = 2 and v₃ = 2 states have been determined, with standard deviations of the fits from 0.00024 to 0.00067 cm⁻¹. The 2ν₁ overtones of F³⁵Cl¹⁶O₃ and F³⁷Cl¹⁶O₃ are perturbed by an A₁/E Coriolis resonance between the v₁ = 2 state and one E component of the v₄ = 1, v₆ = 2 manifold. The 2ν₂ of F³⁷Cl¹⁸O₃ is perturbed by the same kind of interaction involving the v₁ = v₆ = 1 (E) state, at about 1396 cm⁻¹. In these bands the resonance is localized on rotational levels with specific J and K values. As a consequence, a few transitions of the perpendicular bands involving the interacting levels could be identified in the spectra. A simultaneous fit of the transitions assigned to the dyads has been performed and the parameters of the excited states have been determined, including the high order Coriolis interaction coefficient . The anharmonic constants x₁₁, x₂₂, x₃₃ of all the studied isotopologues of FClO₃, x₄₆ of F³⁵Cl¹⁶O₃, x₄₆ + g₄₆ of F³⁷Cl¹⁶O₃ and x₁₆ of F³⁷Cl¹⁸O₃, have been derived.     

Magnetotransport properties and magnetocaloric effect in La0.67Ca0.33Mn1−xTMxO3 (TM=Cu,Zn) perovskite manganites

The magnetic and transport properties of the perovskites La_0.67Ca_0.33Mn_1-xTM_xO₃ were found to be sufficiently changed with the substitution of Mn-sites by other 3d transition-metal cations (TM=Cu,Zn; x=0.15). The values of T_C, T_M−I, and T_CMR were surveyed when Mn was replaced by Cu and Zn. The magnetic field induced resistivity and magnetic entropy change of these samples showed abrupt changes near T_C (194.2 and 201.5 K for Cu and Zn-doped case respectively) and attained the highest values among the doped cases (up to 20% Cu). The maximum values (obtained at H=4 kOe) of magnetoresistance ratio (CMR) were 27.8%, and 24.5% and of magnetic entropy change (−ΔS_M) were 3.9 and 3.2 J/kg K for Cu and Zn-doped, respectively.     

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.     

DC and AC conductivities of (As2S3)100−x(AsSe0.5Te0.5I)x chalcogenide glasses

The DC and AC conductivities of samples from the system (As₂S₃)_100−x(AsSe_0.5Te_0.5I)_x, where x=0, 5, 10, 15, 20, 25, 30, 35, 50, 70 and 90 mol%, were measured as a function of temperature. Besides, the AC conductivities of the samples with x=10 and 30 were measured as a function of frequency from room temperature to the glass transition temperature. The DC conductivity dependence on temperature is of the Arrhenius type, whereas the value of the pre-exponential factor suggests the electrical conduction by localized states in the band tails and by localized states near the Fermi level. The small values of the conduction activation energy (10⁻²-10⁻¹ eV) obtained at higher frequencies suggest that the conduction in these materials is due to hopping of charge carriers between close defect states near the Fermi level.     

Temperature dependence of electrical resistivity for Ca-doped perovskite-type Y1−xCaxCoO3 prepared by sol-gel process

The temperature dependences of DC electrical resistivity for perovskite-type oxides Y_1−xCa_xCoO₃ (0?x?0.1), prepared by sol-gel process, were investigated in the temperature range from 20 K up to 305 K. The results indicated that with increase of doping content of Ca the resistivity of Y_1−xCa_xCoO₃ decreased remarkably, which was found to be caused mainly by increase of carrier (hole) concentration. In the whole temperature range investigated the temperature dependence of resistivity ρ(T) for the un-doped (x=0) sample decreased exponentially with decreasing temperature (i.e. ln ρ∝1/T), with a conduction activation energy ; the resisitivity of lightly doped oxide (x=0.01) possessed a similar temperature behavior but has a reduced E_a (0.155 eV). Moreover, experiments showed that the relationship ln ρ∝1/T existed only in high-temperature regime for the heavily doped samples (T?82 and ∼89 K for x=0.05 and 0.1, respectively); at low temperatures Mott's ln ρ∝T^−1/4 law was observed, indicating that heavy doping produced strong random potential, which led to formation of considerable localized states. By fitting of the experimental data to Mott's T^−1/4 law, we estimated the density of localized states N(E_F) at the Fermi level, which was found to increase with increasing doping content.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

DC conductivity of silver vanadium tellurite glasses

The mixed electronic-ionic conduction in 0.5[xAg₂O-(1−x)V₂O₅]-0.5TeO₂ glasses with x=0.1-0.8 has been investigated over a wide temperature range (70-425 K). The mechanism of dc conductivity changes from predominantly electronic to ionic within the 30?mol% Ag₂O?40 range; it is correlated with the underlying change in glass structure. The temperature dependence of electronic conductivity has been analyzed quantitatively to determine the applicability of various models of conduction in amorphous semiconducting glasses. At high temperature, T>θ_D/2 (where θ_D is the Debye temperature) the electronic dc conductivity is due to non-adiabatic small polaron hopping of electrons for 0.1?x?0.5. The density of states at Fermi level is estimated to be N(E_F)≈10¹⁹-10²⁰ eV⁻¹ cm⁻³. The carrier density is of the order of 10¹⁹ cm⁻³, with mobility ≈2.3×10⁻⁷-8.6×10⁻⁹ cm² V⁻¹ s⁻¹ at 300 K. The electronic dc conductivity within the whole range of temperature is best described in terms of Triberis-Friedman percolation model. For 0.6?x?0.8, the predominantly ionic dc conductivity is described well by the Anderson-Stuart model.     

Ac magnetic susceptibility measurements in nanoparticulate powders of iron-doped ZnO

Low temperature (T) ac magnetic susceptibility (χ_ac) measurements were performed in powder samples of the Zn_1−xFe_xO (x=0-0.078) prepared by a combustion reaction method. The amplitude of the ac magnetic field was kept constant (1 mT) while its frequency (f) varied in the range 10-10⁴ Hz for 5≤T≤300 K. The diluted samples presented cusps with maxima distributed around T_f=17.5±0.5 K while no such feature was observed for the pure sample (x=0). The cusp was found to become more pronounced with the increasing Fe content. Also it decreased and shifted to higher values of T by increasing f. The shift in T_f was found to follow a Vogel-Fulcher law with E_a/k_B=317.6 K, T₀=4.65 K and τ₀=10⁻¹⁴ s, for the activation energy, critical temperature and characteristic time-constant, respectively. The energy gap of the sample was measured and they were found to vary in the range 3.75-3.80 eV. The overall χ_ac-data resembles those obtained for cluster spin-glass state.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.     

Photoluminescence investigation of ferromagnetic Ga1−xMnxN layers with GaN templates grown on sapphire (0 0 0 1) substrates

We have investigated the temperature and composition 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. The efficient PL is peaked in the red (1.86 eV), yellow (2.34 eV), and blue (3.29 eV) spectral range. The band-gap energy of the Ga_1−xMn_xN layers decreased with increasing temperature and manganese composition. The band-gap energy of the Ga_1−xMn_xN layers was modeled by the Varshni equation and the parameters were determined to be α = 2.3 × 10⁻⁴, 2.7 × 10⁻⁴, 3.4 × 10⁻⁴ eV/K and β = 210, 210, and 230 K for the manganese composition x = 0.1%, 0.2%, and 0.8%, respectively. As the Mn concentration in the Ga_1−xMn_xN layers increased, the temperature dependence of the band-gap energy was clearly reduced.     

Magnetostriction, Curie temperature and microstructure of Tb0.29(Dy1−xPrx)0.71Fe1.97 oriented alloys

The Tb_0.29(Dy_1−xPr_x)_0.71Fe_1.97 (x=0, 0.1, 0.2 and 0.3) alloys were prepared by directional solidification method. The orientation, magnetostriction λ, Curie temperature T_c and microstructure of alloys were characterized by XRD, standard resistant strain gauge technique, VSM and SEM-EDS. The results reveal that the alloys have a preferred orientation of 〈1 1 0〉 and 〈1 1 3〉 direction when x>0. With the increase in Pr content, the T_c of alloys decreases gradually and the non-cubic phase appears, resulting in the decline of λ dramatically, from 1935.2×10⁻⁶ for x=0 to 695.9×10⁻⁶ for x=0.3 at a compressive stress of 6 MPa and a magnetic field of H=240 kA m⁻¹.     

Magnetic and transport properties of granular and Heusler-type glass-coated microwires

We studied magnetic and structural properties of granular Co_xCu_100−x (5<x<40 at%), Cu₆₃Fe₃₇ and Heusler-type Ni₂MnGa glass-coated microwires. We found that the structure of Co–Cu microwires consists of two phases: fcc Cu for all the samples and fcc α-Co present for higher Co content. In the case of low Co content, Co atoms are distributed within the Cu matrix. The quantity and the size of grains strongly depend on the geometry of the microwire. Co–Cu and Fe–Cu microwires exhibited considerable magnetoresistance (MR). For Co_xCu_100−x microwires at x≥30 the anisotropic contribution to MR has been observed. Temperature dependences of magnetization measured without an external magnetic field (ZFC) and in the presence of a field (FC) show considerable difference below 20 K, indicating the presence of small α-Fe or Co grains embedded in the Cu matrix. Annealed Ni₂MnGa microwires showed ferromagnetic behavior with Curie temperature about 330 K and polycrystalline structure with space group I4/mmm and lattice parameters a=3.75 Å and c=6.78 Å.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Effect of heating rates on microstructure and superconducting properties of pure MgB2

The influence of different heating rates, ranging from 5 to 30 K min⁻¹, on the microstructure and superconducting of the MgB₂ bulk was investigated. No obvious variation in the grain size was found for the samples heated from 5 K min⁻¹ to 20 K min⁻¹ except for the changes in morphologies. Moreover, the grain refinement was obtained under the heating rate of 30 K min⁻¹. The critical current density (J_c) suggested that the 5 K min⁻¹ sample had the best performance in high field. Here, the differential thermal analysis (DTA) was employed to analyze the kinetics of MgB₂ phase formation with the different heating rates. The results showed that the large amount of MgB₂ formed at low temperature, which lead to compact structures under the slow heating rate. The fast heating rate would promote the evaporation of Mg at high temperature, which was considered to generate the vacancy and impurities in the sample.     

Metamagnetic transition and magnetocaloric effect in charge-ordered Pr0.68Ca0.32−xSrxMnO3 (x=0, 0.1, 0.18, 0.26 and 0.32) compounds

In this study, magnetic and magnetocaloric properties of Pr_0.68Ca_0.32−xSr_xMnO₃ (x=0, 0.1, 0.18, 0.26 and 0.32) compounds were investigated. X-ray results indicated that all the samples have a single phase of orthorhombic symmetry. The orthorhombic unit cell parameters increase with the increase in Sr content. Large negative magnetic entropy changes (−26.2 J/kg K at 38 K and 5 T for x=0 and −6.5 J/kg K at 83 K and 6 T for x=0.1) were attributed to ultrasharp metamagnetic transitions. The peak value of ΔS_m decreased from −4.1 J/kg K for x=0.18 sample to −2.4 J/kg K for x=0.32 at 1 T magnetic field.     

Spectroscopic investigations of neodymium cyclotriphosphates

In the framework of systematic investigations in the properties of rare-earth cyclotriphosphates, polycristalline samples of La_1−xNd_xP₃O₉·3H₂O have been synthesized with x=5×10⁻³, 10⁻², 5×10⁻², 10⁻¹ and 1. Absorbance spectra were measured at 300 K in the 300-1000 nm region. Fluorescent emissions from the ⁴F_3/2 multiplet were observed at 300 and 6 K under pulsed laser excitations in either the ⁴F_7/2 or ⁴F_3/2 multiplet and the decays of these emissions were measured. These decays are exponential with decay-times on the order of 100 ns for all values of x. No important lengthening is observed as either the Nd concentration is decreased from 100 to 0.5 at% or the temperature is lowered from 300 to 6 K. These results are in contradiction with those obtained for the anhydrous La_1−xNd_x(PO₃)₃ compounds prepared by progressively heating the corresponding La_1−xNd_xP₃O₉·3H₂O powder materials, a fact which shows the predominant role played by the water molecules in the Nd³⁺ luminescence in the considered hydrated compounds.     

Modification of Cd1−xMnxTe crystal surface layers by nanopulsed laser irradiation

The surface modification of Cd_1−xMn_xTe (x = 0-0.3) crystal wafers under pulsed laser irradiation has been studied. The samples were irradiated by a Q-switched ruby laser with pulse duration of 80 ns. Optical diagnostics of laser-induced thermal processes were carried out by means of time-resolved reflectivity measurements at wavelengths 0.53 and 1.06 μm. Laser irradiation energy density, E varied in the range of 0.1-0.6 J/cm². Morphology of irradiated surface was studied using scanning electron microscopy. The energy density whereby the sample surface starts to melt, depends on Mn content and is equal to 0.12-0.14 J/cm² for x ≤ 0.2, in the case of x = 0.3 this value is about 0.35 J/cm². The higher Mn content leads to higher melt duration. The morphology of laser irradiated surface changes from a weakly modified surface to a single crystal strained one, with an increase in E. Under irradiation with E in the range of 0.21-0.25 J/cm², the oriented filamentary crystallization is observed. The Te inclusions on the surface are revealed after the irradiation of samples with small content of Mn.     

Exchange bias in bulk Ni-Mn-In-based Heusler alloys

The crystal structure and exchange bias of the bulk Heusler alloys Ni₅₀Mn_50−xIn_x with 14.5?x?15.2 have been investigated using X-ray diffraction and magnetization measurements, respectively. Magnetic measurements were performed with SQUID magnetometry after samples were zero-field cooled and field cooled (FC) in positive magnetic fields up to H=50 kOe, from a temperature T=380 K. Three temperatures of the phase transitions, T₁<T_M<T_C, and a shift of the FC (50 kOe) magnetic hysteresis loops up to 120 Oe at 5 K have been detected for all samples. The exchange bias field (H_E) was almost constant for intermediate In concentrations 14.8<x<15.2, and sharply decreased to about 20 Oe on the borders of this concentration interval (x?14.5; 15.2?x). The changes of H_E have been related to changes in the ratio of T₁ to T_M: the overlapping of transitions at T₁ and T_M (for x=14.8, and 15.2) results in a decrease in H_E.