The interplay between the lattice and magnetism in La（Fe11.4Al1.6）C0.02 studied by powder neutron diffraction

The crystallographic structure and magnetic properties of La（Fell.4Alz.6）C0.02 are studied by magnetic measurernent and powder neutron diffraction with temperature and applied magnetic field. Rietveld refinement shows that La（Fe11.4Al1.6）C0.02 crystallizes into the cubic NaZn13-type with two different Fe sites： FeI （8b） and FeII （96i）, and that A1 atoms preferentially occupy the FeII site. A ferromagnetic state can he induced at a medial temperature of 39 K-139 K by an external magnetic field of 0.7 T, and a large lattice is correspondingly found at 100 K and 0.7 T. In all other conditions, La（Fe11.4Al1.6）C0.02 has no net magnetization in the paramagnetic （T 〉 TN = 182 K） or antifer- romagnetic states, and thus keeps its small lattice. Analysis of the Fe Fe bond length indicates that the ferromagnetic state prefers longer Fe-Fe distances.     

The phase transition,hygroscopicity, and thermal expansion properties of Yb_2-xAl_xMo₃O₁₂

Materials with the formula Yb 2-xAlxMo3O12(x =0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1.0, 1.1, 1.3, 1.5, and 1.8) were synthesized and their structures, phase transitions, and hygroscopicity investigated using X-ray powder diffrac- tion, Raman spectroscopy, and thermal analysis. It is shown that Yb2-xAlxMo3O12 solid solutions crystallize in a single monoclinic phase for 1.7 ≤ x ≤ 2.0 and in a single orthorhombic phase for 0.0 ≤ x ≤ 0.4, and exhibit the characteristics of both monoclinic and orthorhombic structures outside these compositional ranges. The monoclinic to orthorhombic phase transition temperature of Al2Mo3O12 can be reduced by partial substitution of Al 3+ by Yb3+, and the Yb2-x AlxMo3O12 (0.0 < x ≤ 2.0) materials are hydrated at room temperature and contain two kinds of water species. One of these interacts strongly with and hinders the motions of the polyhedra, while the other does not. The partial substitution of Al3+ for Yb3+ in Yb2Mo3O12 decreases its hygroscopicity, and the linear thermal expansion co- efficients after complete removal of water species are measured to be 9.1×10 6 /K, 5.5×10 6 /K, 5.74×10 6 /K, and 9.5 × 10 6 /K for Yb1.8 Al0.2 (MoO4)3 , Yb1.6Al0.4 (MoO4 )3, Yb0.4 Al1.6 (MoO4)3 , and Yb 0.2Al1.8 (MoO4)3 , respectively.     

Valence and magnetic states of impurity iron ions in the La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Co<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> perovskite

The local magnetic and valence states of impurity iron ions in the rhombohedral La_0.75Sr_0.25Co_0.98 ⁵⁷Fe_0.02O₃ perovskite were studied using Mössbauer spectroscopy in the temperature range 87–293 K. The Mössbauer spectra are described by a single doublet at 215–293 K. The spectra contained a paramagnetic and a ferromagnetic component at 180–212 K and only a broad ferromagnetic sextet at T < 180 K. The results of the studies showed that, over the temperature range 87–295 K, the iron ions are in a single (tetrahedral) state with a valence of +3. In the temperature range 180–212 K, two magnetic states of Fe³⁺ ions were observed, one of which is in magnetically ordered microregions and the other, in paramagnetic microregions; these states are due to atomic heterogeneity. In the magnetically ordered microregions in the temperature range 87–212 K, the magnetic state of the iron ions is described well by a single state with an average spin S = 1.4 ± 0.2 and a magnetic moment μ(Fe) = 2.6 ± 0.4μ _B .     

Amorphous-crystalline dual-layer structures resulting from metastable liquid phase separation in(Fe₅₀Co₂₅B₁₅Si₁₀)₈₀Cu₂₀ melt-spun ribbons

(Fe50Co25B15Si10)80Cu20 ribbons are prepared by using the single-roller melt-spinning method.A dual-layer structure consisting of a(Fe,Co)-rich amorphous phase and a Cu-rich crystalline phase forms due to metastable liquid phase separation before solidification.The magnetic hysteresis loops of the as-quenched and annealed samples are measured at room temperature.It is indicated that the coercivity of the ribbon is almost zero in the as-quenched state.The crystallization leads to the increase of coercivity and decrease of saturation magnetization.     

Evolution of the 251 cm^-1 infrared phonon mode with temperature in Ba_0.6K_0.4Fe₂As₂

The far-infrared optical reflectivity of an optimally doped Ba1-xKxFe2As2(x =0.4) single crystal is measured from room temperature down to 4 K. We study the temperature dependence of the in-plane infrared-active phonon at 251 cm-1 . This phonon exhibits a symmetric line shape in the optical conductivity, suggesting that the coupling between the phonon and the electronic background is weak. Upon cooling down, the frequency of this phonon continuously increases, following the conventional temperature dependence expected in the absence of a structural or magnetic transition. The intensity of this phonon is temperature independent within the measurement accuracy. These observations indicate that the structural and magnetic phase transition might be completely suppressed by chemical doping in the optimally doped Ba0.6K0.4Fe2As2 compound.     

Improved multiferroic properties of La-doped 0.6BiFeO₃-0.4SrTiO₃ solid solution ceramics

The 0.6(Bi1-xLax)FeO 3-0.4SrTiO 3(x = 0,0.1) multiferroic ceramics are prepared by a modified Pechini method to study the effect of substitution of SrTiO3 and La in BiFeO3.The X-ray diffraction patterns confirm the single phase characteristics of all the compositions each with a rhombohedral structure.The magnetic properties of the ceramics are significantly improved by a solid solution with SrTiO3 and substitution of La.The values of the dielectric constant ε r and loss tangent tan δ of all the samples decrease with increasing frequency and become constant at room temperature.The La-doped 0.6BiFeO3-0.4SrTiO3 ceramics exhibit improved dielectric and ferroelectric properties,with higher dielectric constant enhanced remnant polarization(Pr) and lower leakage current at room temperature.Compared with a anti-ferromagnetic BiFeO3 compound,the 0.6(Bi0.9La0.1)FeO3-0.4SrTiO3 sample shows the optimal ferromagnetism with remnant magnetization M r ～ 0.135 emμ/g and ferroelectricity with Pr ～ 5.94 μC/cm 2 at room temperature.     

Thermal properties of high-k Hf_1-xSi_xO₂

Classical atomistic simulations based on the lattice dynamics theory and the Born core-shell model are performed to systematically study the crystal structure and thermal properties of high-k Hf1-xSixO2 . The coefficients of thermal expansion, specific heat, Grneisen parameters, phonon densities of states and Debye temperatures are calculated at different temperatures and for different Si-doping concentrations. With the increase of the Si-doping concentration, the lattice constant decreases. At the same time, both the coefficient of thermal expansion and the specific heat at a constant volume of Hf1-xSixO2 also decreases. The Grneisen parameter is about 0.95 at temperatures less than 100 K. Compared with Si-doped HfO2 , pure HfO2 has a higher Debye temperature when the temperature is less than 25 K, while it has lower Debye temperature when the temperature is higher than 50 K. Some simulation results fit well with the experimental data. We expect that our results will be helpful for understanding the local lattice structure and thermal properties of Hf1-xSixO2 .     

The magnetic properties of diluted CoFe₂O₄ nanomaterials

The magnetic properties of (Cox Fe1-x )A(Zn1-xFe1+x) BO4 are studied using mean-field theory and the probability distribution law to obtain the saturation magnetization, the coercive field, the critical temperature, and the exchange interactions with different values of D (nm) and x. High-temperature series expansions (HTSEs) combined with the Pad′e approximant are used to calculate the critical temperature of (Cox Fe1-x) A (Zn1-x Fe1+x) BO4 , and the critical exponent associated with magnetic susceptibility is obtained.     

GREAT MAGNETIC ENTROPY CHANGE IN La(Fe, M)13 (M=Si, Al) WITH Co DOPING

Very large magnetic entropy change Δ S_M, which originates from a fully reversible second-order transition at Curie temperature T_C, has been discovered in compounds La(Fe, Si)₁₃, La(Fe, Al)₁₃ and those with Co doping. The maximum change ΔS_M\approx19 J·kg^-1·K^-1, achieved in LaFe_11.4Si_1.6 at 209K upon a 5T magnetic field change, exceeds that of Gd by more than a factor of 2. The T_C of the Co-doped compounds shifts to higher temperatures. ΔS_M still has a considerable large magnitude near room temperature. The phenomena of very large ΔS_M, convenience of adjustment of T_C, and also thesuperiority of low cost, strongly suggest that the compounds La(Fe, M)₁₃ (M=Si, Al) with Co doping are suitable candidates for magnetic refrigerants at high temperatures.     

A comparative study of magnetic and dielectric behaviors for La(1-x)Bi(x)Mn(1-y)Fe(y)O3 series (with x = 0.5, 0.7 and y = 0.3, 0.7)

We have carried out an extensive investigation into the effect of doping on both the A- and B-sites for the multiferroic La(0.5)Bi(0.5)Mn(0.5)Fe(0.5)O(3) in relation to its physical properties. The temperature dependent magnetization and dielectric response are determined for different percentages of Bi- and Fe-substitutions. For La(0.5)Bi(0.5)Mn(0.7)Fe(0.3)O(3), there is a prominent ferromagnetic transition T(C) around 110 K, whereas the other La(0.5)Bi(0.5)Mn(0.3)Fe(0.7)O(3) and La(0.3)Bi(0.7)Mn(0.3)Fe(0.7)O(3) phases fail to exhibit any clear transition. On the other hand, for the Fe-rich phases, the coercive field increases to 2450 Oe compared to 1720 Oe (for the Mn-rich phase). All the compositions exhibit coexistence of ferromagnetic and antiferromagnetic phases at low temperatures. The temperature dependent dielectric constant of the investigated samples varies from 32,000 to 500 at room temperature and the data has been analyzed using the universal dielectric response model.     

LaFe11.4Al1.6中铁磁相与反铁磁相的双相共存

通过磁场下热磁曲线的测量，在LaFe114Al16化合物中发现了一个在一定温区内随温度稳定的铁磁相和反铁磁相的共存亚稳态.确定了这个亚稳态能够存在的磁场和温度范围，从而使LaFe114Al16化合物的磁相图更加完善.这个亚稳态的温度稳定性能够很好地解释磁性转变的临界场随温度的变化行为.这个双相共存亚稳态的存在，与LaFe114Al16中的磁性交换作用及晶格畸变所产生的边界相的稳定性有关. 关键词： 共存相 亚稳态 晶格畸变     

New magnetic states in copper metaborate CuB<Subscript>2</Subscript>O<Subscript>4</Subscript>

The static and resonance properties of copper metaborate CuB₂O₄ were experimentally studied in a magnetic field applied in the crystal tetragonal plane. The field-induced second-order phase transition to a weakly ferromagnetic state was observed in the temperature range 10–20 K. The low-field state is characterized by the absence of spontaneous moment, and it represents, presumably, a long-period helicoid. At temperatures below 2 K, two sequential first-order phase transitions were observed. They were accompanied by jumps in resonance absorption with a hysteresis upon changing field-scan direction. These transitions can be caused by the transformation of the incommensurate spin structure into the helicoidal states with periods commensurate with the lattice translation period.     

EPR Features of Spin-Crossover in Tris(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dialkyl-Dithiocarbamato)Iron(III)

The temperature dependence of electron paramagnetic resonance (EPR) spectra of a series of dithiocarbamates Fe(RR′dtc)₃ was studied in the temperature range from 5 to 300 K. A small part of solvated complexes serving as spin probes in the EPR-silent matrix enabled the observation of EPR of the Fe(III) ion in the whole temperature range. The spin transition was revealed in the reduction of the integral intensity of the signal from the high-spin complexes and in the non-monotonous change of the line width with temperature decrease due to the effect of the low-spin complexes with short spin–lattice relaxation times. Below ca. 60 K, the ferromagnetic ordering of the magnetic moments in low-spin particles (“domains”) arising at the spin transition was observed.     

Structural anomalies associated with the electronic and spin transitions in LnCoO<Subscript>3</Subscript>

A powder X-ray diffraction study, combined with magnetic susceptibility and electric transport measurements, was performed on a series of LnCoO₃ perovskites (Ln = Y, Dy, Gd, Sm, Nd, Pr and La) over a temperature range 100–1000 K. A non-standard temperature dependence of the observed thermal expansion was modelled as a sum of three contributions: (1) weighted sum of lattice expansions of the cobaltite in the diamagnetic low spin state and in the intermediate (IS) or high (HS) spin state. (2) An anomalous expansion due to the increasing population of excited (IS or HS) states of Co³⁺ ions over the course of the diamagnetic-paramagnetic transition. (3) An anomalous expansion due to excitations of Co³⁺ ions to another paramagnetic state accompanied by an insulator-metal transition. The anomalous expansion is governed by parameters that are found to vary linearly with the Ln ionic radius. In the case of the first magnetic transition it is the energy splitting E between the ground low spin state and the excited state, presumably the intermediate spin state. The energy splitting E, determined by a fit to magnetic susceptibility, decreases with temperature. The values of E determined for LaCoO₃ and YCoO₃ at T=0 K are 164 K and 2875 K respectively, which fall to zero at T=230 K for LaCoO₃ and 860 K for YCoO₃. The second anomalous expansion connected with a simultaneous magnetic and insulator-metal transition is characterized by its center at T=535 K for LaCoO₃ and 800 K for YCoO₃. The change of the unit cell volume during each transition is independent of the Ln cation and is about 1% in both cases.     

Magnetotransport characteristics of strained La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> epitaxial manganite films

The electrical and magnetic characteristics of La_0.7Sr_0.3MnO₃ (LSMO) epitaxial manganite films are investigated by different methods under conditions when the crystal structure is strongly strained as a result of mismatch between the lattice parameters of the LSMO crystal and the substrate. Substrates with lattice parameters larger and smaller than the nominal lattice parameter of the LSMO crystal are used in experiments. It is shown that the behavior of the temperature dependence of the electrical resistance for the films in the low-temperature range does not depend on the strain of the film and agrees well with the results obtained from the calculations with allowance made for the interaction of electrons with magnetic excitations in the framework of the double-exchange model for systems with strongly correlated electronic states. Investigations of the magneto- optical Kerr effect have revealed that an insignificant (0.3%) orthorhombic distortion of the cubic lattice in the plane of the NdGaO₃(110) substrate leads to uniaxial anisotropy of the magnetization of the film, with the easy-magnetization axis lying in the substrate plane. However, LSMO films on substrates (((LaAlO₃)_0.3+(Sr₂AlTaO₆)_0.7)(001)) ensuring minimum strain of the films exhibit a biaxial anisotropy typical of cubic crystals. The study of the ferromagnetic resonance lines at a frequency of 9.76 GHz confirms the results of magnetooptical investigations and indicates that the ferromagnetic phase in the LSMO films is weakly inhomogeneous.     

Magnetic entropy change and magnetic phase transition of LaFe11.4Al1.6Cx （x=0-0.8） compounds

The unit cell volume and phase transition temperature of LaFe11.4Al1.6Cx compounds have been studied. The magnetic entropy change, refrigerant capacity and the type of magnetic phase transition are investigated in detail for LaFe11.4Al1.6Cx with x=0.1, All the LaFe11.4Al1.6Cx （x=0-0.8） compounds have the cubic NaZn13-type structure. The addition of carbon atoms brings about a considerable increase in the lattice parameter. The bulk expansion results in the change of phase transition temperature （Tc）, Tc increases from 187K to 269 K with x varying from 0.1 to 0.8, Meanwhile an increase in the lattice parameter can also cause a change of the magnetic ground state from antiferromagnetic to ferromagnetic. Large magnetic entropy change IASI is found over a large temperature range around Tc and the refrigerant capacity is about 322J/kg for LaFe11.4Al1.6C0.1. The magnetic phase transition belongs in weakly first-order one for x=0.1.     

Multiple magnetic transitions in single crystals of Ce<Subscript>12</Subscript>Fe<Subscript>57.5</Subscript>As<Subscript>41</Subscript> and La<Subscript>12</Subscript>Fe<Subscript>57.5</Subscript>As<Subscript>41</Subscript>

Measurements of magnetic and transport properties were performed on needle-shaped single crystals of Ce₁₂Fe_57.5As₄₁ and La₁₂Fe_57.5As₄₁. The availability of a complete set of data enabled a side-by-side comparison between these two rare earth compounds. Both compounds exhibited multiple magnetic orders within 2–300 K and metamagnetic transitions at various fields. Ferromagnetic transitions with Curie temperatures of 100 and 125 K were found for Ce₁₂Fe_57.5As₄₁ and La₁₂Fe_57.5As₄₁, respectively, followed by antiferromagnetic type spin reorientations near Curie temperatures. The magnetic properties underwent complex evolution in the magnetic field for both compounds. An antiferromagnetic phase transition at about 60 K and 0.2 T was observed merely for Ce₁₂Fe_57.5As₄₁. The field-induced magnetic phase transition occurred from antiferromagnetic to ferromagnetic structure. A strong magnetocrystalline anisotropy was evident from magnetization measurements of Ce₁₂Fe_57.5As₄₁. A temperature-field phase diagram was present for these two rare earth systems. In addition, a logarithmic temperature dependence of electrical resistivity was observed in the two compounds within a large temperature range of 150–300 K, which is rarely found in 3D-based compounds. It may be related to Kondo scattering described by independent localized Fe 3d moments interacting with conduction electrons.     

Field-induced ferromagnetic order and colossal magnetoresistance in La(1.2)Sr(1.8)Mn2O7: a 139La NMR study

In order to gain insights into the origin of colossal magnetoresistance (CMR) in manganese oxides, we performed a 139La NMR study in the double-layered compound La(1.2)Sr(1.8)Mn2O7. We find that above the Curie temperature T(C) = 126 K, applying a magnetic field induces a long-range ferromagnetic order that persists up to T = 330 K. The critical field at which the induced magnetic moment is saturated coincides with the field at which the CMR effect reaches a maximum. Our results therefore indicate that the CMR observed above T(C) in this compound is due to the field-induced ferromagnetism that produces a metallic state via the double exchange interaction.     

Phase coexistence in NaZn13-type LaFe11.4Al1.6C0.02 compound

In NaZn₁₃-type LaFe_11.4Al_1.6C_0.02 compound, a signature of weak ferromagnetism is observed at ∼100 K under a low field by ac magnetic-susceptibility and electrical-resistivity measurements, implying the coexistence of ferromagnetic (FM) and antiferromagnetic (AFM) phases. The hysteresis in isofield magnetization curves and large magnetic relaxation demonstrate the metastability of the magnetic state in the AFM-FM transition region. The variations of magnetization with temperature, time and field show distinct step-like behaviors, which is probably attributed to the discontinuous growth of ferromagnetic cluster in antiferromagnetic matrix.     

Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.