Magnetic properties of the compounds N(CH3)4MnIIMIII(CN)6 ·8 H2O(MIII = Mn,Fe)

In the isostructural cyanobridged chain compounds N(CH₃)₄Mn^IIM^III(CN)₆ · 8H₂O high spin Mn(II) ions couple antiferromagnetically to low spin Mn(III) of Fe(III) ions. The Mn^II–Mn^III compound orders ferrimagnetically below T_N = 28.5 ± 1 K. The tetragonal a and b axes are easy ones for the magnetic moments. In the Mn^II–Fe^III compound antiferromagnetic order occurs below T_N = 9.3 K, with spins aligned along the tetragonal c axis. The compound undergoes a meta-magnetic transition from the antiferromagnetic to a ferrimagnetic phase. This occurs at 2 K for a field H_crit ≈ 1.2 T. The temperature dependence of H_crit, which vanishes at T_N, is followed. The tricritical temperature T¹ is ～ 5 K.     

Room temperature magnetoresistance in Ln2/3A1/3MnO3 manganites

The investigation of the manganites La_2/3−xPr_xSr_1/3MnO₃, La_2/3Sr_1/3−xCa_xMnO₃ and La_2/3+xCa_1/3−2xAg_xMnO₃, which all exhibit Mn³⁺:Mn⁴⁺=2, shows that it is possible to reach high magnetoresistance at room temperature, up to 21% under 1.2 T. These materials are compared to La_5/6Ag_1/6MnO₃ which corresponds to the same Mn³⁺:Mn⁴⁺ ratio and exhibits a magnetoresistance of 25% in this field. An interesting feature deals with the value of the insulator-metal transition temperature T_IM, often higher than T_C, especially for Ag-based compounds. It is suggested that the latter results either from a better oxygenation of the surface of the grains or from a migration of silver toward the surface.     

Electronic transport properties of stuffed compositions of ferromagnetic copper chromium telluride: Cu1+xCr2Te4 (x=0-1)

We present here a detailed study of electronic transport properties of the metallic-ferromagnetic compounds Cu_1+xCr₂Te₄, having excess Cu atoms with x=0-1, from 2 to 400 K. The stuffing of the copper atoms in the parent structure reduces the ferromagnetic ordering temperature T_C from 325 to 156 K, while for the entire range the dependence of the electrical resistance and the thermopower with temperature and the anomalies in them on the magnetic ordering remain similar. All the compounds show a magnon-drag contribution in thermopower as a positive maximum around T_C/3, and a T² - dependence of resistivity at low temperatures. The increasing effects of the short range magnetic ordering in the paramagnetic resistivity are seen with the increase in the stuffing of atoms in these compounds. The transport properties are explained by the current carriers —the holes in a wide energy band dominated by the p-state of Te-atoms, which are scattered by the spindisorder in the paramagnetic phase and from the magnons in the ferromagnetic phase.     

Magnetic and electrical transport properties in the self-doped manganite La0.9Mn0.9M0.1O3 (M=Mn,Zn and Ti)

The magnetic and electrical transport properties of La_0.9Mn_0.9M_0.1O₃ (M=Mn, Zn and Ti) were investigated. The temperature and magnetic field dependence of electrical resistivity (ρ) and dc magnetization were studied. All the compounds are found in rhombohedral structure. The excess oxygen in all three compounds was detected through iodometric titration. A modification in resistivity is observed when M=Mn is replaced by M=Zn and Ti. The high temperature resistivity above T_C follow variable range hopping model for both Zn and Ti compounds. For Zn doping, the observation of large field-cool effect and decrease in resistivity at room temperature and is assumed to be due to the implant of Mn⁴⁺ in Mn³⁺ matrix, which favor Mn³⁺/Mn⁴⁺ double exchange. The ferromagnetic behavior below T_C for the compound with M=Ti is correlated to the excess oxygen in it, which implants Mn⁴⁺ and thus incorporates ferromagnetic interactions. The substitutions lead to a reduction of T_c and magnetization.     

B NMR relaxation in superconductors: YRuB2 and LuRuB2

To investigate the electronic states in YRuB₂ and LuRuB₂, we have carried out ¹¹B NMR measurements. In the normal state, the spin-lattice relaxation rates 1/T₁'s in these compounds are proportional to the temperature T. 1/T₁'s show a small coherence peak just below the superconducting transition temperature T_c and decrease exponentially well below T_c. YRuB₂ and LuRuB₂ are found to be BCS superconductors with the energy gap 2Δ(0)=3.52 k_BT_c.     

Spin reversal and magnetization jumps in ErMexMn1−xO3 perovskites (Me=Ni,Co)

The erbium-based manganite ErMnO₃ has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni)=0.2–0.5 in the nickel-based solid solution ErNi_xMn_1−xO₃, while it can be extended up to x(Co)=0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co³⁺. Presence of different magnetic entities (i.e., Er³⁺, Ni²⁺, Co²⁺, Co³⁺, Mn³⁺, and Mn⁴⁺) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNi_xMn_1−xO₃, a critical concentration x_crit(Ni)=1/3 separates two regimes: spin-canted AF interactions predominate at x<x_crit, while the ferromagnetic behavior is enhanced for x>x_crit. Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at T_c, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T⁻¹, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo_0.50Mn_0.50O₃ was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50=Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co²⁺ and Co³⁺ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Local structure study of T′ cuprate superconductors

Undoped T′-type cuprates are believed to be charge transfer (Mott-Hubbard) insulators. Recent observation of undoped superconducting T′-type cuprates suggests half-filling weakly correlated metallic electron states (Tsukada et al.), which is against the fundamental picture. Here we report the local structures of undoped T′-(La³⁺,Y³⁺)₂CuO₄ and doped T′-(La³⁺,Ce⁴⁺)₂CuO₄ thin-film single crystals by polarized extended X-ray absorption fine structure (EXAS). The in-plane (E//ab) polarized Cu K-EXAFS data shows a remarkable Cu-O bond distance displacement. The broadened Cu-O distribution suggests a large local lattice distortion in T′-type structures, which might influence the electronic structure.     

Analysis of low temperature specific heat in Nd0.5Sr0.5MnO3 and R0.5Ca0.5MnO3 (R=Nd,Sm, Dy and Ho) compounds

We report on the specific heat C(T) of doped manganites Nd_0.5Sr_0.5MnO₃, Nd_0.5Ca_0.5MnO₃, Sm_0.5Ca_0.5MnO₃, Dy_0.5Ca_0.5MnO₃ and Ho_0.5Ca_0.5MnO₃ in the temperature range 2?T?300 K using modified rigid ion model (MRIM). The present specific heat results are in general satisfactory agreement with experimental data except at very low temperatures (i.e. T?12 K). Also a sharp peak observed in the experimental results for these compounds around 5 K could not be revealed by our computed results as they arise due to Schottky-like anomaly. Besides, we have reported the cohesive and the thermal properties of these compounds. The results obtained by us are discussed in detail.     

The Tc-SSR correlation in A3B(A15-type) compounds

The 28A₃B(A15-type) compounds, for which both the phase equilibrium diagram and the superconducting critical temperature, T_c, are known, can be divided into two groups. The first group consists of compounds whose SSR (solid solution range) is either zero or extends only to the A-rich side of the stoichiometric composition. The second group consists of the compounds whose SSR extends to both sides or only to the B-rich side. The first group of compounds generally has high T_c's and follow the T_c-SSR correlation proposed earlier.Both the grouping and the T_c-SSR correlation are directly relatable to “A-chain integrity” and thus lend further support to the thesis that “A-chain integrity” is of fundamental importance in the superconductivity of these compounds.     

Heat capacity of Heusler alloys: Ferromagnetic Ni2MnSb,Ni2MnSn,NiMnSb and antiferromagnetic CuMnSb

We report the results of the investigation of the specific heat of the ferromagnetic Heusler Ni₂MnSn, Ni₂MnSb, NiMnSb and antiferromagnetic CuMnSb alloys. The low-temperature behaviour of the specific heat may be described as C=γT+βT³ for ferromagnetic compounds and as C=γT+δ T²+βT³ for antiferromagnetic CuMnSb. The values of the density of states from the heat capacity measurements are higher than those from electronic band structure calculations. Debye temperatures are in a good agreement with those obtained from thermal expansion measurements. The Grüneisen parameter is calculated for Ni₂MnSn and CuMnSb from the magnetic contribution to the specific heat in the vicinity of T_C or T_N.     

Spin-state transition, magnetic, electrical and thermal transport properties of the perovskite cobalt oxide Gd0.7Sr0.3CoO3

The magnetization, resistivity ρ, thermoelectric power (TEP) S, and thermal conductivity κ in perovskite cobalt oxide Gd_0.7Sr_0.3CoO₃ have been investigated systematically. Based on the temperature dependence of susceptibility χ_g(T) and Seebeck coefficient S(T), a combination of the intermediate-spin (IS) state for Co³⁺ and the low-spin (LS) state for Co⁴⁺ can be suggested. A metal-insulator transition (MIT) caused by the hopping of σ* electrons (localized or delocalized e_g electrons) from the IS Co³⁺ to the LS Co⁴⁺ is observed. Meanwhile, S(T) curve also displays an obvious phonon drag effect. In addition, based on the analysis of the temperature dependence of S(T) and ρ(T), the high-temperature small polaron conduction and the low-temperature variable-range-hopping conduction are suggested, respectively. As to thermal conduction κ(T), rather low κ values in the whole measured temperature range is attributed to unusually large local Jahn-Teller (JT) distortion of Co³⁺O₆ octahedra with IS state.     

NIR luminescence from Er/Yb, Tm/Yb, Er/Tm and Nd ions-doped zincborotellurite glasses for optical amplification

In this paper, we report the near-infrared luminescence from the Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped TeO₂-ZnO-B₂O₃-Li₂O-Na₂O glasses for optical amplification. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) profiles of the host glass matrix have been carried out. From the DSC thermogram, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The near-infrared spectra of Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped glasses have shown full-width at half-maxima (FWHM) around 58, 127, 87 and 35 nm, respectively. These glasses with better thermal stability and broad near-infrared emissions should have potential applications in broadly tunable laser sources and broadband optical amplification at low-loss telecommunication windows.     

Room temperature magnetic entropy change and magnetoresistance in La0.70(Ca0.30−xSrx)MnO3:Ag 10% (x=0.0−0.10)

The magnetic and magnetocaloric properties of polycrystalline La_0.70(Ca_0.30−xSr_x)MnO₃:Ag 10% manganite have been investigated. All compositions are crystallized in single phase orthorhombic Pbnm space group. Both, the insulator–metal transition temperature (T^IM) and Curie temperature (T_c) are observed at 298 K for x=0.10 composition. Though both T^IM and T_c are nearly unchanged with Ag addition, the MR is increased. The MR at 300 K is found to be as large as 31% with magnetic field change of 1 T, whereas it reaches up to 49% at magnetic field of 3 T for the La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample. The maximum entropy change (ΔS_Mmax) at near its T_c (300.5 K) is 7.6 J kg⁻¹ K⁻¹ upon the magnetic field change of 5 T. The La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample having good MR (31%^1 T, 49%^3 T) and reasonable change in magnetic entropy (7.6 J kg⁻¹.K⁻¹, 5 T) at 300 K can be a potential magnetic refrigerant material at ambient temperatures.     

Thermal expansion of ZrFe2 and some rare-earth iron compounds

The thermal expansion coefficient of the compounds ZrFe₂, TiFe₂, YFe₂, ErFe₂, ErFe₃, Er₆Fe₂₃ and Er₂Fe₁₇ has been determined from room temperature up to 700°C. The anomalous thermal expansion of some of these compounds observed at temperatures below their Curie temperature (T_c) is shown to be related to a strong pressure dependence of T_c. (dT_c/dP is large and negative).     

Optical absorption spectrum of PrCl3 complexes in solution

Optical spectral studies of Pr³⁺ in PrCl₃ complexes with MgCl₂, CaCl₂, CdCl₂ and NH₄Cl have been carried out, and the second derivative spectra of these five Pr³⁺ complexes are reported. From the observed features of the ³P₂ and ¹D₂ bands, crystal field (A₂₀, A₄₀) parameters were evaluated assuming C_3h symmetry for Pr³⁺ in these complexes. The Slater-Condon(F₂, F₄ and F₆), configuration interaction (α, β) and spin-orbit (ξ_4?), Racah (E¹,E² and E³), nephelauxetic (β), bonding (δ) and Judd-Ofelt (T₂, T₄ and T₆) intensity parameters are evaluated. Theoretical estimates of spectral intensities calculated from Judd-Ofelt and electric (S_ed)-magnetic (S_md) dipole linestrength methods are in good agreement with the observed values. The radiative lifetimes of elctronic excited states ³P₁, ³P₀, and ¹D₂ of Pr³⁺ in these five different hosts have been theoretically estimated.     

H nuclear magnetic resonance study of the ferroelastic and superionic phase transitions of (NH4)4LiH3(SO4)4 single crystals

We investigated the temperature dependences of the line shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in (NH₄)₄LiH₃(SO₄)₄ single crystals. On the basis of the data obtained, we were able to distinguish the “ammonium” and “hydrogen-bond” protons in the crystals. For both the ammonium and hydrogen-bond protons in (NH₄)₄LiH₃(SO₄)₄, the curves of T₁ and T₂ versus temperature changed significantly near the ferroelastic and superionic phase transitions at T_C (=232 K) and T_S (=405 K), respectively. In particular, near T_S, the ¹H signal due to the hydrogen-bond protons abruptly narrowed and the T₂ value for these protons abruptly increased, indicating that these protons play an important role in this superionic phase transition. The marked increase in the T₂ of the hydrogen-bond protons above T_S indicates that the breaking of O-H?O bonds and the formation of new H-bonds with HSO₄^- contribute significantly to the high-temperature conductivity of (NH₄)₄LiH₃(SO₄)₄ crystals.     

metamagnetic behavior of linear chain pyridine compounds: Co(Pyridine)2Cl2, Fe(Pyridine)2Cl2, Fe(Pyridine)2(NCS)2 and Ni(Pyridine)2Cl2

Magnetic phase transitions in the pyridine (pyr) compounds Co(pyr)₂Cl₂, Fe(pyr)₂Cl₂, Fe(pyr)₂(NCS)₂ and Ni(pyr)₂Cl₂ have been observed at applied magnetic fields of ～0.7, 0.7, 1.1 and 2.7 kG respectively. These low field phase transitions are observed in the Fe and Ni compounds at T = 4.2 K, and in the Co compound at T < 3K, and are consistent with metamagnetic behavior. Magnetic saturation is not achieved in any of these compounds for fields of 60 kG, reflecting high anisotropy.     

NMR investigation of the layered transition metal phosphorus trichalcogenides and the intercalation compounds LixNiPS3

The transition metal phosphorus trichalcogenides MPX₃ are layered semiconductors which can be intercalated either chemically or electrochemically by lithium atoms. We present a NMR study of the magnetic properties of the MPX₃ compounds (M = Ni, Mn, Fe; X = S, Se) and their modification as a function of intercalation in the compounds Li_xNiPS₃ (x = 0 ? 1.29). In the concentration range x = 0.02 ? 0.5, the relative shift of the P³¹ resonance line K_iso = -0.052 % and the Neel temperature T_N = 155 K are constant and barely different from that measured in pure NiPS₃ (K_iso = -0.057 %, T_N = 165 K). For x > 0.5 a new P³¹ resonance line is observed, which grows with x at the expense of the previous one. It corresponds to non magnetic layers $\text{S - Ni}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{(P}{}_2\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{- S}$, which progressively replace the paramagnetic ones up to the limit of intercalation x = 1.29. Investigation of the lithium ions mobility through Zeeman and dipolar spin lattice relaxation times T_1～ and T_1D measurements indicates a very low self-diffusion coefficient - D = 10^-13 ? 10^-14cms^-1 -, that is four orders of magnitude smaller than those measured in Li_xTiS₂ compounds. This strongly contrasts with the good electrochemical activity of the Li_xNiPS₃ system.     

Anomalous nuclear spin relaxation in liquid 3He4He mixtures

The longitudinal relaxation time, T₁, was measured in liquid ³He⁴He mixtures with molar concentrations of ³He of 0.12, 0.20 and 0.45 under saturated vapor pressure. λ-anomaly was clearly observed in the temperature dependence of T₁.