Structural phase transition in the 2D spin dimer compound SrCu 2 ( BO 3 ) 2

A displacive, 2nd order structural phase transition at T _s = 395 K from space group I 2 m below T _s to I 4/m c m above T _s has been discovered in the two-dimensional spin dimer compound SrCu₂(BO₃)₂. The temperature evolution of the structure in both phases has been studied by X-ray diffraction and Raman scattering, supplemented by differential scanning calorimetry and SQUID magnetometry. The implications of this transition and of the observed phonon anomalies in Raman scattering for spin-phonon and interlayer coupling in this quantum spin system will be discussed. Received 24 July 2000 and Received in final form 2 November 2000     

Preparation of Cu 2 O nanoparticles dispersed in NH 2 -terminated polyethyleneoxide matrix

Small Copper (I) oxide, Cu₂O, nanoparticles dispersed in diamine-terminated polyethyleneoxide (PEO-NH₂) matrix have been successfully prepared by vacuum evaporation of copper onto the molten PEO-NH₂. The obtained composite were characterized by TEM, electron diffraction, TG-DTA and FT-IR spectroscopy. The stable composite, in which the Cu₂O nanoparticles are stabilized through interaction between NH₂ chain end groups of PEO molecules and Cu₂O nanoparticles was obtained when the samples were heat-treated at 110 ^° C. The mean size of the Cu₂O nanoparticles increased from 2.5 to 3.5 nm in diameter upon increasing the amount of initial Cu deposition. The obtained composite material having a waxy texture was soluble in many solvents without aggregation and can be handled as a simple chemical compound for starting material in various applications. Received 29 November 2000     

Unconventional field and angle dependences of the Shubnikov-de Haas oscillations spectra in the quasi two-dimensional organic superconductor (BEDO-TTF) 2ReO 4H 2O

We report on the inter-layer oscillatory conductance of the two-dimensional organic superconductor (BEDO-TTF)₂ReO₄H₂O measured in static and pulsed magnetic fields of up to 15 and 52 T, respectively. In agreement with previous in-plane studies, two Shubnikov-de Haas oscillation series linked to the two electron and the hole orbits are observed. The influence of the magnitude and orientation of the magnetic field with respect to the conducting plane is studied in the framework of the conventional two- and three-dimensional Lifshits-Kosevich (LK) model. Deviations of the data from this model are observed in low fields strongly tilted with respect to the normal to the conducting plane. In this latter case, the observed behaviour is consistent with an unexplained lowering of the cyclotron effective mass. At high magnetic field, the oscillatory data could have been compatible with the occurrence of a magnetic breakdown orbit built from the hole and electron orbits. However, the increase of the cyclotron effective mass, linked to the electron orbits, as the magnetic field increases above ∼12 T is consistent with a field-induced phase transition. In the lower field range, where the conventional LK model holds, the analysis of the angle dependence of the oscillations amplitude suggests significant renormalisation of the effective Landé factor. Received 22 August 2000 and Received in final form 20 December 2000     

Crystal and magnetic structures of the oxyphosphates MFePO 5 (M = Fe, Co, Ni, Cu). Analysis of the magnetic ground state in terms of superexchange interactions

We have studied in detail the crystal and magnetic structures of the oxyphosphates MFePO₅ (M: divalent transition metal) using neutron powder diffraction as a function of temperature. All of them are isomorphic to the mixed valence compound α-Fe₂PO₅ with space-group Pnma. No disorder exists between the two metallic sites. The M²⁺O₆ octahedra share edges between them and faces with Fe³⁺O₆ octahedra building zigzag chains running parallel to the b-axis that are connected by PO₄ tetrahedra. The topology of this structure gives rise to a complex pattern of super-exchange interactions responsible of the observed antiferromagnetic order. The magnetic structures are all collinear with the spin directed along the b-axis except for M = Co. The experimental magnetic moments of Cu⁺² and Ni²⁺ correspond to the expected ionic value, on the contrary the magnetic moment of Fe³⁺ is reduced, probably due to covalence effects, and that of Co²⁺ is greater than the spin-only value indicating a non negligible orbital contribution. Using numerical calculations we have established a magnetic phase diagram adapted for this type of crystal structure and determined the constraints to be satisfied by the values of the exchange interactions in order to obtain the observed magnetic structure as the ground state. Received 15 December 2000 and Received in final form 25 June 2001     

Magnetic structure and anisotropy of YFe 6 Ga 6 and HoFe 6 Ga 6

The magnetic structure of RFe₆Ga₆ intermetallic compounds with R = Y, Ho have been determined by neutron powder diffraction, ⁵⁷Fe M?ssbauer spectroscopy, AC susceptibility, TGA (Thermo-Gravimetric Analysis) and magnetization measurements. Both compounds crystallize in the tetragonal ThMn₁₂ structure (space group I4/mmm) with the magnetic structure of YFe₆Ga₆ consisting of a simple ferromagnetic alignment of Fe moments in the basal plane with a Curie temperature of 475(5) K. Gallium atoms are found to fully occupy the 8i site, with Fe and Ga atoms equally distributed over the 8j site, whilst Fe atoms fully occupy the 8f site. The average Fe moments are 1.68(10) and 1.46(10) at 15 and 293 K, respectively. The average room temperature Fe magnetic moments determined by neutron diffraction are in overall agreement with the average Fe moment deduced from M?ssbauer spectroscopy and bulk magnetization measurements on this compound. The magnetic anisotropy of the compound HoFe₆Ga₆ is also planar in the temperature range 6-290 K, with Ho magnetic moments of 9.28(20) and 2.50(20) at 6 K and 290 K, respectively, coupled anti-ferromagnetically to the Fe sublattice and a Curie temperature of 460(10) K. The magneto-crystalline anisotropies of both compounds are comparable at low temperatures. Received 8 March 2001 and Received in final form 18 June 2001     

Magnetic properties of the cyclic spincluster Fe6:bicine

The magnetic properties of the cyclic compound [Fe₆(bicine)₆] LiClO₄ ^. 2MeOH are reported. The cluster Fe₆(bicine)₆ forms an antiferromagnetically coupled ring structure of Fe ^III ions. The magnetic susceptibility is measured between 2 and 300 K and yields the exchange coupling of J/k _B = - 27.5±0.5 K. The field dependence of the magnetic moment is studied at 3 and 6 K in magnetic fields up to 5 T. The zero-field splitting of the first excited spin states with S = 2 and 3 are determined by ESR at 94 GHz. The intra-molecular interactions of the Fe ^III ions are analyzed and the on-site anisotropy of the Fe ^III due to the ligand-configuration is determined to d /k _B = - 0.633±0.008K. Received 28 October 2002 / Received in final form 22 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: bernd@piobelix.physik.uni-karlsruhe.de     

Composite spin-triplet superconductivity in an symmetric lattice model

The two-channel Anderson lattice model which has SU (2) ⊗ SU (2) symmetry is of relevance to understanding of the magnetic, quadrupolar and superconducting phases in U_1-xTh_xBe₁₃ or Pr based skutterudite compounds such as PrFe₄P₁₂ or PrOs₄Sb₁₂. Possible unconventional superconducting phases of the model are explored. They are characterized by a composite order parameter comprising of a local magnetic or quadrupolar moment and a triplet conduction electron Cooper-pair. This binding of local degrees of freedom removes the entropy of the non Fermi-liquid normal state. We find superconducting transitions in the intermediate valence regime which are suppressed in the stable moment regime. The gap function is non analytic and odd in frequency: a pseudo-gap develops in the conduction electron density of states which vanishes as |ω| close to ω = 0. In the strong intermediate valent regime, the gap function acquires an additional -dependence. Received 28 February 2002 / Received in final form 18 April 2002 Published online 9 July 2002     

Pseudo-gap and possible Spin-Peierls transition in the vanadium oxide VOSb 2 O 4

We report on the magnetic susceptibility and electron spin resonance measurements on polycrystalline samples of the vanadium oxide VOSb₂O₄, a quasi-one-dimensional S = 1/2 Heisenberg system. The susceptibility vanishes at zero temperature, but there is no cusp at the onset of the susceptibility drop, and the ESR linewidth exhibits an increase characteristic of a phase transition at a much lower temperature. We show that this behaviour is consistent with the formation of a pseudo-gap in a spin-Peierls system in the adiabatic limit. Received 7 February 2001 and Received in final form 24 April 2001     

Electron diffraction and microscopy of single-wall carbon nanotube bundles produced by different methods

The atomic structure of single-wall carbon nanotube bundles produced by three different techniques (laser ablation, electric arc discharge and catalytic chemical vapor deposition (CCVD)) has been characterized by electron diffraction and microscopy. Information on the helicity and the lattice packing has been obtained. Concerning the helicity, small bundles produced by CCVD exhibit only one or two tube helicities within a single bundle. The diffraction patterns of laser-ablation produced bundles also present well-defined but more diversified chiralities within a single bundle. By contrast the data acquired on bundles formed by arc discharge show a more diffuse pattern, characteristic of a random chirality dispersion within a single bundle. Concerning the lattice packing, informations are obtained via a detailed study of the equatorial line of the diffraction pattern for bundles produced by the three techniques. This electron diffraction study is completed by high-resolution electron microscopy. Received 8 August 2001 and Received in final form 14 March 2002     

Neutron diffraction study of the magnetic ordering in the series R 2 BaNiO 5 (R = Rare Earth)

A neutron diffraction study, as a function of temperature, of the title compounds is presented. The whole family (space group Immm, a ≈ 3.8?, b ≈ 5.8?, c ≈ 11.3?) is structurally characterised by the presence of flattened NiO₆ octahedra that form chains along the a-axis, giving rise to a strong Ni-O-Ni antiferromagnetic interaction. Whereas for Y-compound only strong 1D correlations exist above 1.5 K, presenting the Haldane gap characteristic of 1D AF chain with integer spin, 3D AF ordering is established simultaneously for both R and Ni sublattices at temperatures depending on the rare earth size and magnetic moment. The magnetic structures of R₂BaNiO₅ ( R = Nd, Tb, Dy, Ho, Er and Tm) have been determined and refined as a function of temperature. The whole family orders with a magnetic structure characterised by the temperature-independent propagation vector = (1/2, 0, 1/2). At 1.5 K the directions of the magnetic moments differ because of the different anisotropy of the rare earth ions. Except for Tm and Yb (which does not order above 1.5 K), the magnetic moment of the R³⁺ cations are close to the free-ion value. The magnetic moment of Ni²⁺ is around 1.4 , the strong reduction with respect to the free-ion value is probably due to a combination of low-dimensional quantum effects and covalency. The thermal evolution of the magnetic structures from T _N down to 1.5 K is studied in detail. A smooth re-orientation, governed by the magnetic anisotropy of R³⁺, seems to occur below and very close to T _N in some of these compounds: the Ni moment rotates from nearly parallel to the a-axis toward the c-axis following the R moments. We demonstrate that for setting up the 3D magnetic ordering the R-R exchange interactions cannot be neglected. Received 19 July 2001     

Interplay of structural, magnetic and transport properties in thelayered Co-based perovskite LnBaCo 2 O 5 (Ln = Tb, Dy, Ho)

The oxygen deficient cobaltites LnBaCo₂O₅ (Ln = Tb, Dy, Ho) exhibit two successive crystallographic transitions at T _N ∼340 K and at T _CO ∼210 K. Whereas the first transition (P4/mmm to Pmmm) is related to the long-range antiferromagnetic ordering of the Co ions (spin ordering), the second transition (Pmmm to Pmmb) corresponds to the long-range ordering of the Co²⁺ and Co³⁺ species (charge ordering) occurring in 1:1 ratio in the structure. The charge ordered (CO) state was directly evidenced by the observation of additional superstructure peaks using neutron and electron diffraction techniques. The CO state was also confirmed indirectly from refinement of high resolution neutron diffraction data as well as from resistivity and DSC measurements. From the refined saturated magnetic moment values only, ∼3.7 and ∼2.7 , the electronic configuration of the Co ions in LnBaCo₂O₅ remains conjectural. Two pictures, with Co³⁺ ions either in intermediate spin state ( t ⁵ _2g e ¹ _g ) or in high spin state ( t ⁴ _2g e ² _g ), describe equally well our experimental data. In both cases, the observed magnetic structure can be explained using the qualitative Goodenough-Kanamori rules for superexchange. Finally, in contrast to the parent Ln = Y compound [Vogt et al. , Phys. Rev. Lett. 84, 2969 (2000)], we do not report any spin transition in LnBaCo₂O₅ (Ln = Tb, Dy, Ho). Received 13 December 2000     

Magnetic susceptibility in quasi one-dimensional Ba<Subscript>a2</Subscript>V<Subscript>3</Subscript>O<Subscript>9</Subscript>: chain segmentation versus the staggered field effect

A pronounced Curie-like upturn of the magnetic susceptibility χ( T ) of the quasi one-dimensional spin chain compound Ba₂V₃O₉ has been found recently [#!kaul:02!#]. Frequently this is taken as a signature for a staggered field mechanism due to the presence of g-factor anisotropy and Dzyaloshinskii-Moriya interaction. We calculate this contribution within a realistic structure of vanadium 3 d- and oxygen 2 p-orbitals and conclude that this mechanism is far too small to explain experimental results. We propose that the Curie term is rather due to a segmentation of spin chains caused by broken magnetic bonds which leads to uncompensated S = ? spins of segments with odd numbers of spins. Using the finite-temperature Lanczos method we calculate their effective moment and show that ∼ 1% of broken magnetic bonds is sufficient to reproduce the anomalous low-T behavior of χ( T ) in Ba₂V₃O₉. Received 19 December 2002 / Received in final form 29 January 2003 Published online 14 March 2003     

Phase transitions in Co nanoclusters grown by pulsed laser deposition

The crystalline structure of Co clusters embedded in an amorphous Al₂O₃ matrix was studied by transmission electron microscopy (TEM) and electron diffraction (TED). In the first stage of the growth a metastable structure (body-centred-cubic) is observed. A face-centred-cubic phase (fcc) is found when the size of the clusters increases ( diameter > 4 nm). The hexagonal-close-packed phase arises in the fcc phase by a succession of stacking faults at the largest sizes. The mechanisms of phase transformation have been determined by using high resolution electron microscopy (HREM). The chemical nature of the clusters, in particular the existence of Co-O bonds, was investigated by using electron energy loss spectroscopy (EELS). Received 03 July 2000 and Received in final form 22 December 2000     

Magnetoquantum de Haas-van Alphen oscillations in spin-split two-dimensional Fermi liquid

Theory of magnetoquantum oscillations with spin-split structure in strongly anisotropic (two-dimensional (2D)) metal is developed in the formalism of level approach. Parametric method for exact calculation of oscillations wave forms and amplitudes, developed earlier for spin degenerate levels is generalized on a 2D electron system with spin-split levels. General results are proved: 1) proportionality relation between magnetization and chemical potential oscillations accounting for spin-split energy levels and magnetic field unperturbed levels (states of reservoir), 2) basic equation for chemical potential oscillations invariant to various models of 2D and 1D energy bands (intersecting or overlapping) and localized states. Equilibrium transfer of carriers between overlapping 2D and 1D bands, characterizing the band structure of organic quasi 2D metals, is considered. Transfer parameter, calculated in this model to be of the order of unity, confirms the fact that the wave form of oscillations in organic metals should be quasisymmetric up to ultralow temperature. Presented theory accounts for spin-split magnetization oscillations at magnetic field directions tilted relative to the anisotropic axis of a metal. Theoretical results are compared with available experimental data on organic quasi-2D metal α-(BEDT-TTF)₂KHg(SNC)₄ explaining the appearance of clear split structure under the kink magnetic field and absence above by the corresponding change in the electron g-factor rather than cyclotron mass. Received 20 December 2000 and Received in final form 13 July 2001     

Temperature and pressure dependencies of the crystal structure of the organic superconductor (TMTSF) 2 ClO 4

The crystal structure of (TMTSF)₂ClO₄ has been determined at (7 K, 1 bar) and at (7 K, 5 kbar) with a high accuracy. For the latter, low temperature and pressure were applied simultaneously using a X-ray diffraction instrumentation designed in our laboratory, these results are the first for molecular compounds. The effects of lowering the temperature are not the same as those produced by increasing the pressure. At (7 K, 1 bar) the anion ordering which occurs in this compound, and which is characterised by the appearance of b ^* /2 superlattice reflections, is well observed. This anion ordering leads to the presence of two independent stacks of TMTSF cations which is the only case found in the Bechgaard salts family. The comparison of the low temperature crystal structures under atmospheric pressure and at 5 kbar shows that the centres of mass are nearly the same, independent of the pressure: the interchain interactions do not depend on the doubling of the unit cell. Under pressure, the ordering (0, 1/2, 0) does not occur at any temperature. These structural data are confirmed by the quantum chemical calculations which show that the difference in the site energy of the two independent cations is 100 meV. Received 10 April 2000 and Received in final form 27 September 2000     

Magnetic behavior and role of the antiphase boundaries in Fe3O4 epitaxial films sputtered on MgO (001)

Magnetite Fe₃O₄ films were grown on single crystal MgO (001) substrates using facing target sputtering technique. Conversion Electron M?ssbauer Spectroscopy and magneto optical polar Kerr spectra have confirmed the stoichiometric repartition of Fe cations corresponding to the inverse spinel structure and the electronic structure characteristic of bulk Fe₃O₄. Hysteresis loops carried out at room temperature show that, in a 1 T applied magnetic field, only 60% of the saturation magnetization is detected. This behavior is discussed in correlation to the antiphase boundaries (APBs) observed by electron microscopy. Magnetic force microscopy studies show that magnetic domains are larger than the mean distance between APBs. Received 2 July 2001     

Magnetic circular dichroism in Co 2p photoemission of Co/Cu(1 1 13): Separation of the fundamental spectra

We measured high-quality Co 2p magnetic circular dichroism (MCD) spectra in photoemission for > 5 ML Co films grown on Cu(1 1 13) using a “complete” experiment, where the sample magnetization and the light helicity vector were reversed separately. We show how the four measured spectra, M^±P^±, can be used to make new linear combinations, which correspond to the circular dichroism in the angular dependence (CDAD), magnetic linear dichroism in the angular dependence (MLDAD) and MCD spectra. The integrated signals of the MLDAD and CDAD can be used to estimate the error caused by the difference in the degrees of magnetization and light polarization, respectively, in the opposite alignments. The MCD signal integrated over the entire 2p region does not average to zero, as one would have expected from the sum rule for photoemission to a non-interacting continuum state. There is a strong MCD signal in the entire region between the 2p _3/2 and 2p _1/2 main lines with pronounced satellite structure. The differences between the measured and calculated results for an independent-particle and an atomic model indicate the presence of interatomic electron correlation effects and configurational mixing. Received 26 September 2000     

Magnetic oscillations in the 2D network of compensated coupled orbits of the organic metal (BEDT-TTF) 8 Hg 4 Cl 12 (C 6 H 5 Br) 2

Interlayer magnetoresistance and magnetisation of the quasi-two dimensional organic metal (BEDT-TTF)₈Hg₄Cl₁₂(C₆H₅Br)₂ have been investigated in pulsed magnetic fields extending up to 60 T and 33 T, respectively. About fifteen fundamental frequencies, composed of linear combinations of only three basic frequencies, are observed in the oscillatory spectra of the magnetoresistance. The dependencies of the oscillation amplitude on the temperature and on the magnitude and orientation of the magnetic field are analyzed in the framework of the conventional two-dimensional Lifshitz-Kosevitch (LK) model. This model is implemented by damping factors which accounts for the magnetic breakthrough occurring between electron and hole orbits yielding conventional Shubnikov-de Haas closed orbits (model of Falicov and Stachowiak) and quantum interferometers. In particular, a quantum interferometer enclosing an area equal to the first Brillouin zone area is evidenced. The LK model consistently accounts for the temperature and magnetic field dependence of the oscillation amplitude of this interferometer. On the contrary, although this model formally accounts for almost all of the observed oscillatory components, it fails to give consistent quantitative data in most other cases. Received 4 September 2002 / Received in final form 14 November 2002 Published online 27 January 2003 RID="a" ID="a"e-mail: audouard@insa-tlse.fr RID="b" ID="b"UMR 5830: Unité Mixte de Recherche CNRS - Université Paul Sabatier - INSA de Toulouse RID="c" ID="c"UMS 5642: Unité Mixte de Service CNRS - Université Paul Sabatier - INSA de Toulouse     

Effective hyperfine temperature in frustrated Gd 2Sn 2O 7: two level model and 155Gd Mössbauer measurements

Using ¹⁵⁵Gd M?ssbauer spectroscopy down to 27 mK, we show that, in the geometrically frustrated pyrochlore Gd₂Sn₂O₇, the Gd³⁺ hyperfine levels are populated out of equilibrium. From this, we deduce that the hyperfine field, and the correlated Gd³⁺ moments which produce this field, continue to fluctuate as T ↦ 0. With a model of a spin 1/2 system experiencing a magnetic field which reverses randomly in time, we obtain an analytical expression for the steady state probability distribution of the level populations. This distribution is a simple function of the ratio of the nuclear spin relaxation time to the average electronic spin-flip time. In Gd₂Sn₂O₇, we find the two time scales are of the same order of magnitude. We discuss the mechanism giving rise to the nuclear spin relaxation and the influence of the electronic spin fluctuations on the hyperfine specific heat. The corresponding low temperature measurements in Gd₂Ti₂O₇ are presented and discussed. Received 17 October 2001 Published online 6 June 2002     

Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d _f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5^° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot. Received 15 March 2002 and Received in final form 29 April 2002