Antiferroelectric antiferromagnetic type-I multiferroic Cu9O2(SeO3)(4)Cl-6

We report that Cu9O2(SeO3)(4)Cl-6 is a new multiferroic compound. Comprehensive studies of this compound have been carried out on single crystals as well as polycrystalline samples. Magnetic susceptibility chi and specific heat C with H parallel to c axis both reveal an anomaly at T-N = 37 K associated with the long-range antiferromagnetic order. However, no signature of this phase transition is seen with the H parallel to b axis, providing evidence of the anisotropic nature of its magnetic properties. The results of chi measurements are consistent with the temperature evolution of the intensity of magnetic reflections from the neutron diffraction experiments. The magnetic structure derived from neutron scattering measurements shows that half of the Cu(5) ions carry no moments. Furthermore, an anomaly in the dielectric constant near T-N and observable magnetoelectric coupling below T-N are found. At high temperatures, a dielectric peak at T-E = 267 K is identified with no measurable spontaneous polarization below T-E, thereby suggesting an antiferroelectric order. A steplike anomaly seen in chi(T) at T-E hints the weak spin-lattice coupling. Concomitantly, high-resolution temperature-dependent synchrotron x-ray diffraction experiments elucidate a local structural distortion at T-E.

Synthesis, crystal growth and physical properties of the frustrated spin ladder material BiCu2PO6

Shuang Wang

In recent years quantum antiferromagnets with an intrinsically disordered (“spin liquid”) ground state and an energy gap in the spin excitation spectrum have received a great deal of attention. In search for new experimental realizations of spin-ladder and related models, we have embarked upon a new interesting family of low-dimensional materials with the general formula BiCu2AO6 (A = P, V and As). Among them, BiCu2PO6 shows a structure where Cu spins appear to form a two-leg zigzag ladder, which is believed to be a valuable model of a quantum magnet. However, for detailed studies of quantum magnetism, single crystals are indispensible. Therefore, in this thesis, synthesis and characterization of the newly-discovered spin ladder material BiCu2PO6 (BCPO) and its derivatives in the form of powder and single crystal are presented. Polycrystalline samples of Bi(Cu1-xZnx)2PO6 (x= 0.01, 0.02, 0.03, 0.04, 0.05 and 1), Bi1-y(Ca, Sr, La )yCu2PO6 (y = 0.15, 0.5 and 1) and BiCu2(P1-zVz)O6 (z = 1) were synthesized in this work. The solid state synthesis reactions, phase purity and thermal properties of the samples, substitution solubility, and preliminary magnetic susceptibility have been studied by thermal analysis (TG-DTA), X-ray powder diffraction (XRD), and Scanning Electron Microscope (SEM) as well as DC magnetization measurements, respectively. The BiCu2PO6 structure shows a remarkable chemical flexibility and interesting substitution effects. For detailed studies of the magnetic properties, well characterized large single crystals are indispensable. Thus in this thesis, a number of single crystal growth experiments have been performed using the Travelling Solvent Floating Zone method (TSFZ). Under the elaborated crystal growth conditions (growth rate of ~1 mm/h, gas mixture of 20% O2 in Argon, total 3 pressure (6~6.5 bar), high quality cm -size single crystals of Bi(Cu1-xZnx)2PO6 (x = 0, 0.01, 0.03, 0.05) have been successfully grown for the first time. For these crystals phase purity, crystal morphology/orientation, defect density, chemical composition distribution, crystal structure (room temperature and 1.5 K) and single crystal quality were thoroughly studied based on X-ray and neutron powder diffraction, optical and scanning electron microscopy, X-ray/neutron Laue diffraction, ICP-OES/X-ray fluorescence and two-axis neutron diffraction. Moreover, the specific heat Cp (H,T), AC susceptibility χ(H,T) and DC magnetization M(H,T) measurements on well-characterized single crystal samples of the undoped BCPO and 5% Zn-doped BCPO with the field applied along main crystallographic axes were performed in order to study the unique low temperature magnetic behaviour exhibited in this system, such as anisotropy of the magnetic properties, impurity-induced magnetism by the substitution of non-2+ magnetic cations (e.g. Zn ) and frustration. The magnetic phase diagram (H-T) under low field has been constructed. Further results obtained by close collaborators, based on the measurements made on single crystal samples grown in this thesis, including field-induced quantum phase transitions, NMR, Raman studies are attached directly at the end of this thesis.

EPFL2013

Ferromagnetism in Co-7(TeO3)(4)Br-6: A byproduct of complex antiferromagnetic order and single-ion anisotropy

Helmuth Berger, Ivica Zivkovic

Pronounced anisotropy of magnetic properties and complex magnetic order of a new oxi-halide compound Co-7(TeO3)(4)Br-6 has been investigated by powder and single-crystal neutron-diffraction, magnetization, and ac susceptibility techniques. Anisotropy of susceptibility extends far into the paramagnetic temperature range. A principal source of anisotropy are anisotropic properties of the involved octahedrally coordinated single Co2+ ions, as confirmed by angular-overlap-model calculations presented in this work. Incommensurate antiferromagnetic order sets in at T-N=34 K. The propagation vector is strongly temperature dependent reaching k(1)=[0.9458(6),0,0.6026(5)] at 30 K. A transition to a ferrimagnetic structure with k(2)=0 takes place at T-C=27 K. The magnetically ordered phase is characterized by very unusual anisotropy as well: while M-H scans along the b axis reveal spectacularly rectangular but otherwise standard ferromagnetic hysteresis loops, M-H studies along other two principal axes are perfectly reversible, revealing very sharp spin-flop (or spin-flip) transitions, such as in a standard antiferromagnet (or metamagnet). Altogether, the observed magnetic phenomenology is interpreted as an evidence of competing magnetic interactions permeating the system, in particular of the single-ion anisotropy energy and the exchange interactions. Different coordinations of the Co2+ ions involved in the low-symmetry C2/c structure of Co-7(TeO3)(4)Br-6 render the exchange-interaction network very complex by itself. Temperature-dependent changes in the magnetic structure, together with an abrupt emergence of a ferromagnetic component, are ascribed to continual spin reorientations described by a multicomponent, but yet unknown, spin Hamiltonian.

2009

Ferrimagnetic 120 degrees magnetic structure in Cu2OSO4

Helmuth Berger, Virgile Yves Favre, Arnaud Magrez, Henrik Moodysson Rønnow, Romain Sibille, Gregory Scott Tucker, Lin Yang, Ivica Zivkovic

We report magnetic properties of a 3d(9) (Cu2+) magnetic insulator Cu2OSO4 measured on both powder and single crystal. The magnetic atoms of this compound form layers whose geometry can be described either as a system of chains coupled through dimers or as a kagome lattice where every third spin is replaced by a dimer. Specific heat and DC susceptibility show a magnetic transition at 20 K, which is also confirmed by neutron scattering. Magnetic entropy extracted from the specific heat data is consistent with an S = 1/2 degree of freedom per Cu2+, and so is the effective moment extracted from DC susceptibility. The ground state has been identified by means of neutron diffraction on both powder and single crystal and corresponds to an similar to 120 degrees spin structure in which ferromagnetic intradimer alignment results in a net ferrimagnetic moment. No evidence is found for a change in lattice symmetry down to 2 K. Our results suggest that Cu2OSO4 represents a type of model lattice with frustrated interactions where interplay between magnetic order, thermal and quantum fluctuations can be explored.

AMER PHYSICAL SOC2020

Synthesis, crystal growth and physical properties of the frustrated spin ladder material BiCu2PO6

Shuang Wang

EPFL2013