Moment-volume instabilities in alloys with compositions around the C14 laves phase

We measured the thermal expansion and the specific heat of Ti_xFe_100-x alloys with x = 30.5, 32.5 and 35, all with hexagonal C14 laves phase structure (MgZn₂) like TiFe₂, and determine the temperature dependence of the magnetic contributions to the thermal expansion and the specific heat c_mag. For fixed composition and c mag ( T ) show the same type of behavior, demonstrating that both anomalies are of the same microscopic nature. They originate from moment-volume fluctuations (antiferromagnetic Invar-effect) as a comparison with total energy calculations as a function of atomic volume and moment for TiFe₂ reveals. Received: 26 January 1998 / Accepted: 17 April 1998     

Martensitic transformations: first-principles calculations combined with molecular-dynamics simulations

Results are presented of first-principles total-energy calculations and molecular-dynamics simulations of structural transformations in magnetic transition metal alloys like Fe_1-xNi_x. While first-principles calculations allow to identify those structures having the lower total energy, molecular-dynamics simulations can be used to trace out the dependence of the transformation on temperature, composition, concentration of defects etc. We have used the method of the semi-empiric embedded-atom potential in the molecular-dynamics simulations which yields remarkable good results for the structural changes. Received: 3 February 1998 / Revised: 4 May 1998 / Accepted: 24 June 1998     

A Raman and dielectric study of ferroelectric ceramics

Dielectric and Raman scattering experiments were performed on various ceramics with composition Ba(Ti_1-xZr_x)O₃. Such lead-free, environmental-friendly materials were shown, from dielectric measurements, to exhibit behaviours extending from conventional to relaxor ferroelectrics on increasing the zirconium concentration. The evolution of the Raman spectra was studied as a function of temperature for various compositions, and the spectroscopic signature of the corresponding phases was determined. In the relaxor state, the variation of the integrated intensity of the Raman lines with temperature showed a plateau at low temperature. This anomaly was also detected as a peak in depolarization current measurements, and attributed to ergodicity breaking which characterizes usual relaxor systems. Raman results hint at locally rhombohedral polar nanoregions resulting from the random fields associated with Zr ions. Received 25 September 1998     

Size dependence of dielectric properties and structural metastability in ferroelectrics

The size effect of the dielectric properties and the barrier height was investigated in the ferroelectric solid solution Ba_xSr_1-xTiO₃ system. The decrease of the grain size causes the suppression of the ferroelectricity, and the increase of the relaxation frequency. Barrier heights increase with increasing grain size. The result is analogous to magnetic phase transitions in nanocrystals and other solid-solid phase transitions in nanocrystals. It suggests a general rule that may be of use in the discovery of new metastable phases. An explanation of this phenomenon was given by an electric potential model that agrees well with the experimental results. For Ba_xSr_1-xTiO₃ system, the decrease of xcauses the decrease of the barrier height. Received 3 August 1998 and Received in final form 22 November 1998     

Experimental determination and modelization of a unique phase diagram: solid solutions of antiferromagnetic organometallic radical cation salts

The physical properties of paramagnetic Mo(V) organometallic radical cation salts, , are investigated through the study of two series of solid solutions incorporating two kinds of anions ( or ). The combination of EPR and X-ray diffraction is used to specify the nature of the structural phase transitions which occur in the paramagnetic phase and to determine the corresponding ( T , x ) phase diagrams. Finally, antiferromagnetic resonance is studied to probe the low temperature antiferromagnetic ground state. In the last part of the paper, the observed complex phase diagram is analyzed by considering a compressible model with at least two independent modes of compression. We conclude that the larger compressibilities are associated with the smaller anions. Received 5 August 1998     

A new scaling analysis of the susceptibility and the specific heat of the non-Fermi liquid system with and 0.5

The usual scaling equations at a phase transition, employed out of their usual validity range, with T_c a negative constant, fit properties observed in correlated electron systems with unmatched accuracy. We illustrate this behavior with our data in Ce(Ru_1-xRh_x)₂Si₂ for x = 0.4 and 0.5 and comment these results and what they imply physically. Received 22 June 1998 and Received in final form 29 September 1998     

Charge ordering-disordering in the Th-doped CaMnO3

The structural transitions that appear in the manganites Ca_1-xTh_xMnO₃ versus temperature are studied in connection with their magnetic and transport properties, and compared to those of the Ca_1-xLn_xMnO₃ manganites. An orthorhombic to monoclinic transition is observed for low x values (;this structural distortion, also observed for Ln-doped oxides, is related to the magnetoresistance properties. For higher x values (), modulated commensurate and incommensurate phases are obtained at low temperature, with , b =2 a p and , which are related to Mn³⁺/Mn⁴⁺ charge ordering (CO) phenomena. T values, determined from electron diffraction, are in agreement with those determined from the M ( T ) curves. The low temperature electron microscopy shows that the CO in those oxides is more complex than in Ln-doped manganites. In particular, the destabilisation of CO and consequently of the antiferromagnetic interactions is evidenced as the thorium content increases which may explain the appearance of a spin-glass like behavior for higher x values not seen for Ca_1-xSm_xMnO₃ phases . Received 2 November 1998     

Defect-induced increase in the phonon energy involved in the formation of Urbach tail in Cu-ternaries

From a combined analysis of the stoichiometric composition and Urbach tail in samples of CuInSe₂, CuInTe₂, and CuGaTe₂ of the I-III-VI₂ family of chalcopyrite semiconductors, it is found that the energy hν_p involved in the electron/exciton-phonon interaction is a linear function of a parameter Δz which is the sum of the deviations from ideal molecularity Δx and anion to cation ratio Δy. It gives evidence that in the copper ternaries hν_p is associated to the structural defects caused by cation-cation, cation-anion, and other intrinsic disorders. The high value of hν_p found in the studied samples, higher than the highest optical mode, is shown to come from the contribution of the additional phonon energy due to structural defects. This is in agreement with recently proposed models of the temperature dependence of the Urbach energy.     

Investigations on the soft-mode mechanism of the ferroelectric phase transition in

Dielectric and Raman spectroscopic measurements have been performed to investigate the ferroelectric phase transition in . Single crystals were grown by the zone melting method. The frequency dependence of the dielectric permittivity from 1 MHz to 1 GHz has been studied in a temperature range between 265 and 285 K. A Debye like dielectric dispersion was found, showing a critical slowing down around K. Polarized Raman spectra have been taken between 220 and 310 K. Two softening modes have been found, one of A- and another one of B / B g-symmetry. The phase transition mechanism in can be classified as partially order-disorder and partially displacive, confirming former structural results. It resembles strongly that of monoclinic . Received: 7 April 1998 / Revised: 5 June 1998 / Accepted: 16 June 1998     

Electric quadrupole interactions and the γ–α phase transition in Ce: the role of conduction electrons

We present a theoretical model of the “isostructural" - phase transition in Ce which is based on quadrupolar interactions due to coupled charge density fluctuations of 4f electrons and of conduction electrons. The latter are treated in tight-binding approximation. The - transition is described as an orientational ordering of quadrupolar electronic densities in a structure. The quadrupolar order of the conduction electron densities is complementary to the quadrupolar order of 4f electron densities. The inclusion of conduction electrons leads to an increase of the lattice contraction at the - transition in comparison to the sole effect of 4f electrons. We calculate the Bragg scattering law and suggest synchrotron radiation experiments in order to check the structure. Received 21 September 1999 and Received in final form 2 May 2000     

Investigations of the sublattice magnetizations M(T) in antiferromagnets with fourth-order exchange interactions: EuSrTe

We present a neutron scattering study of the temperature and composition dependence of the MnO-type superstructure reflection intensities in the diamagnetically diluted antiferromagnetic compounds Eu_xSr_1-xTe. In these materials antiferromagnetic biquadratic and ferromagnetic three-spin interactions have been identified recently. These fourth-order non-Heisenberg interactions are able to create their own order parameter which is believed to govern the order of the transverse moment components and which, hence, is directed perpendicular to the common Heisenberg order parameter. The observed MnO-type diffraction intensities originate in the sublattice magnetizations, , of both order parameters. Due to the different composition dependencies for biquadratic interaction processes and three-spin interaction processes , the ferromagnetic three-spin interactions dominate for x > x c =0.85, while for x <0.85 the antiferromagnetic biquadratic interactions dominate. Associated with this sign change in the fourth-order interaction sum the transverse order parameter changes from the antiferromagnetic MnO type for x <0.85 to ferromagnetic for x >0.85. This is noticed as a sudden decrease of the low-temperature MnO scattering intensities at x c =0.85. Although susceptibility measurements reveal clearly a ferromagnetic component for x >0.85 no ferromagnetic Bragg intensities were observed in standard neutron scattering spectra using EuTe powder samples. We explain this by the competition of antiferromagnetic biquadratic and ferromagnetic three-spin interactions whereby a disturbed ferromagnetic superstructure may be generated which gives rise also to weak MnO-type diffraction lines. It is found that the resulting obeys a T² law until a temperature as large as 0.75T_N irrespective of the nature of the transverse order parameter. The T² law must, hence, be common to both types of order parameter showing that the fourth-order interactions re-define the spin dynamics of both completely. From the linear composition dependence of the normalized T² coefficient the existence of three-spin interactions is again confirmed. Received 23 July 1998 and Received in final form 12 October 1998     

Magnetic order and transport in the heavy-fermion system CeCuAu

We report on extensive elastic neutron scattering to determine the wave vector of the magnetic order in CeCu_6-xAu_x single crystals for x > 0.1. For all values of x investigated (0.2, 0.3, 0.5, 1.0) we find long-range incommensurate antiferromagnetic order with an ordering vector (0.625 0.275) for x =0.2, nearly unchanged for x =0.3, and (0.59) for x =0.5, staying roughly the same for x =1.0. In addition, short-range correlations are observed for x =0.2, reminiscent of those found previously for x =0.1. The ordered magnetic moment is found to increase rapidly for small x, and more slowly for the larger x values. The increase of the specific-heat anomaly at the ordering temperature with x is in qualitative accord with this behavior. Finally, data of the electrical resistivity for current flow along the three crystallographic directions are presented, showing a clear signature of the magnetic order. A theoretical interpretation of the interplay of magnetic order and transport in terms of (i) the partial suppression of the Kondo effect by the staggered magnetization and (ii) the anisotropic band structure induced by the staggered field is shown to account well for the data, provided the ordering vector is close to 2 k F, where k F is a typical Fermi momentum. Received: 20 February 1998 / Accepted: 17 April 1998     

SR evidence of low frequency spin fluctuations in the AF phase of hole-doped NiO

μSR measurements in the antiferromagnetic (AF) phase of Ni_1-xLi_xO for are reported. While in pure NiO the muon longitudinal depolarization rate is found almost temperature independent, in the Li-doped compounds broad maxima around 130 K are observed. These maxima are associated with the progressive freezing of the spin fluctuations of S =1/2 defects induced by the localization of the extra-holes. From the temperature dependence of and the stretched exponential form of the depolarization, insights on the distribution of correlation times for the fluctuating field at the muon site are derived. Received: 27 April 1998 / Received in final form and Accepted: 21 August 1998     

Thermodynamic properties of the spin-1/2 antiferromagnetic ladder under magnetic field

Specific heat (C_V) measurements in the spin-1/2 Cu₂(C₂H₁₂N₂)₂Cl₄ system under a magnetic field up to H =8.25 T are reported and compared to the results of numerical calculations based on the 2-leg antiferromagnetic Heisenberg ladder. While the temperature dependences of both the susceptibility and the low-field specific heat are accurately reproduced by this model, deviations are observed above the critical field H_C1 at which the spin gap closes. In this Quantum High Field phase, the contribution of the low-energy quantum fluctuations are stronger than in the Heisenberg ladder model. We argue that this enhancement can be attributed to dynamical lattice fluctuations. Finally, we show that such a Heisenberg ladder, for H > H C1, is unstable, when coupled to the 3D lattice, against a lattice distortion. These results provide an alternative explanation for the observed low temperature ( K-0.8 K) phase (previously interpreted as a 3D magnetic ordering) as a new type of incommensurate gapped state. Received: 23 July 1998 / Accepted: 24 August 1998     

Suppression of antiferromagnetic correlations by quenched dipole-type impurities

The effects of quenched dipole moments on a two-dimensional Heisenberg antiferromagnet are found exactly, by applying the renormalization group to the appropriate classical non-linear sigma model. Such dipole moments represent random fields with power law correlations. At low temperatures, they also represent the long range effects of quenched random strong ferromagnetic bonds on the antiferromagnetic correlation length, , of a two-dimensional Heisenberg antiferromagnet. It is found that the antiferromagnetic long range order is destroyed for any non-zero concentration, x, of the dipolar defects, even at zero temperature. Below a line , where T is the temperature, is independent of T, and decreases exponentially with x. At higher temperatures, it decays exponentially with , with an effective stiffness constant , which decreases with increasing x/T. The latter behavior is the same as for annealed dipole moments, and we use our quenched results to interpolate between the two types of averaging for the problem of ferromagnetic bonds in an antiferromagnet. The results are used to estimate the three-dimensional Néel temperature of a lamellar system with weakly coupled planes, which decays linearly with x at small concentrations, and drops precipitously at a critical concentration. These predictions are shown to reproduce successfully several of the prominent features of experiments on slightly doped copper oxides. Received 22 October 1998     

Soft modes and phonon interactions in studied by neutron scattering

The low frequency lattice dynamics and its relationship to the second order paraelectric-to-ferroelectric transition in Sn₂P₂S₆ is studied. The dispersion branches of the acoustic and lowest lying optical phonons in the a^*-c^* plane have been obtained in the ferroelectric phase, for x-polarized phonons. Close to the phase transition a considerable softening is found for the lowest optical mode (P_x), comparable to the behaviour observed in previous Raman investigations. As found previously in Sn₂P₂Se₆, a strong coupling between the TO(P_x) and TA(u_xz) phonons is observed, although, apparently, not strong enough to lead to an incommensurate phase. The soft TO(P_x) mode at the zone center is observed. The temperature dependence of its frequency and damping shows that the transition is not entirely displacive. At low temperatures an unusual apparent negative LO-TO splitting is observed which is shown to arise from the coupling of the x-polarized soft mode to the nearby z-polarized optical phonon. For comparison, the soft TO(P_x) dispersion in the a^*-b^* plane is measured in both the paraelectric and ferroelectric phases. Consistent frequency changes and LO-TO splitting are observed, revealing a significant interaction between the TA(u_yx) and LA(u_xx) acoustics branches and the TO and LO soft optic branches, respectively. In contrast, the nearby y-polarized optic branch shows almost no temperature dependence. Finally, the influence of piezoelectric effects on the limiting acoustic slopes in the ferroelectric phase is discussed. Received: 11 May 1998 / Revised and Accepted: 15 June 1998     

Structural study of the ferroelectric instability in SnPSe

The structural change occurring in between the paraelectric and the ferroelectric phases is investigated by means of X-ray diffraction. Details of the structure in both phases are obtained and the role of the lone pair is discussed in the light of structural data. In agreement with the 2/ m to m symmetry lowering, polar displacements are found within the m plane away from a particular crystallographic direction but antiparallel displacements occur also. These results are discussed in the frame of the phenomenological theory which predicts a particular temperature dependence of the dielectric polarization in this crystal. Received: 10 July 1998     

Interface polarons in a realistic heterojunction potential

The ground states of interface polarons in a realistic heterojunction potential are investigated by considering the bulk and the interface optical phonon influence. A self-consistent heterojunction potential is used and an LLP-like method is adopted to obtain the polaron effect. The numerical computation has been done for the Zn_1-xCd_xSe/ZnSe system to obtain the polaron ground state energy, self energy and effective mass parallel to the interface. A simplified coherent potential approximation is developed to obtain the parameters of the ternary mixed crystal and the energy band offset of the heterojunction. It is found that at small Cd concentration the bulk longitudinal optical phonons give the main contribution for lower areal electron densities, whereas the interface phonon contribution is dominant for higher areal electron densities. The interface polaron effect is weaker than the effect obtained by the three dimensional bulk phonon and by the two dimensional interface phonon models. Received 17 September 1998     

Magnetic and crystallographic characteristics of Th6–xYxMn23 alloys

Crystallographic studies of Th_6–xY_xMn₂₃ ternaries show that Y₆Mn₂₃ and Th₆Mn₂₃ are miscible in all proportions with lattice parameters that are essentially independent of composition. Magnetic properties of the ternaries have been examined over the temperature range 4 to 500 K. The Curie temperatures and the saturation magnetizations decrease monotonically with decreasing Y content; magnetic ordering is observed for all compositions within the range 1.50 < x ? 6. Since the Mn-Mn spacing is nearly invariant with composition, it follows that electron concentration variation is responsible for the compositional variation of magnetic properties.     

Evolution of charge ordering in manganites

Charge ordering phenomena in the manganites Ca_1-xSm_xMnO₃ have been studied for , using electron diffraction and lattice imaging, completed by magnetic and transport measurements. Three domains can be distinguished, depending on the nature of the structural transitions with temperature. For , the structural transition from a pseudo-tetragonal to a monoclinic form, with decreasing temperature, coincides with the competition between ferromagnetism and antiferromagnetism that is characterized by the temperature T_peak on the M ( T ) curves; short-range charge ordering is observed for manganites. For the second domain, , a structural transition from an orthorhombic to a long-range charge ordered state is clearly observed with decreasing temperature. The corresponding temperature T_CO coincides with the temperature T_peak deduced from magnetic measurements. This long range charge ordering, which appears along a, is either commensurate or incommensurate depending on the x value, with a modulation vector, q being close to x. These modulated superstructures correspond to a stacking of single Mn³⁺ stripes with multiple Mn⁴⁺ stripes along a, either in a commensurate or in an incommensurate manner. The third domain , is characterized by a transition to a charge ordered state with commensurate superstructure at low temperature. The latter can be described as a “partially” charge ordered state in which single “Mn³⁺” stripes alternate with mixed “Mn³⁺/Mn⁴⁺” stripes. Received 17 June 1998