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Mixed-anion compounds, which incorporate multiple types of anions into materials, displays tailored crystal structures and physical/chemical properties, garnering immense interests in various applications such as batteries, catalysis, photovoltaics, and thermoelectrics. However, detailed studies regarding correlations between crystal structure, chemical bonding, and thermal/vibrational properties are rare for these compounds, which limits the exploration of mixed-anion compounds for associated thermal applications. In this work, we investigate the lattice dynamics and thermal transport properties of the metal chalcohalides, CuBiSCl2. A high-purity polycrystalline CuBiSCl2 sample, successfully synthesized via modified solid-state synthetic method, exhibits a low lattice thermal conductivity of 0.9-0.6 W m-1 K-1 from 300 to 573 K. By combining various experimental techniques including 3D electron diffraction with theoretical calculations, we elucidate the origin of low lattice thermal conductivity in CuBiSCl2. The stereo-chemical activity of the 6s2 lone pair of Bi3+ favors an asymmetric environment with neighboring anions involving both short and long bond lengths. This particularity often implies weak bonding, low structure dimensionality, and strong anharmonicity, leading to low lattice thermal conductivity. In addition, the strong two-fold linear S-Cu-S coordination with weak Cu -- Cl interactions induces large anisotropic vibration of Cu or structural disorder, which enables strong phonon-phonon scattering and decreases lattice thermal conductivity. The investigations into lattice dynamics and thermal transport properties of CuBiSCl2 broadens the scope of the existing mixed-anion compounds suitable for the associated thermal applications, offering a new avenue for the search of low thermal conductivity materials in low-cost mixed-anion compounds.

The lattice dynamics of the superconducting materials LaFeSiH and LaFeSiO as well as their intermetallic precursor LaFeSi are investigated by polarized Raman spectroscopy and first-principles calculations, together with X-ray and advanced electron diffraction techniques for their structural analysis. We find that the Fe-dominated Raman-active modes reflect the chemical peculiarities of these silicides compared to their pnictide counterparts, with enhanced structural couplings between the FeSi layer and the spacer that can be related to the ionic vs covalent character of the latter. In addition, we find signatures of enhanced electron-phonon coupling for some of the Raman-active modes. Beyond that, our study reveals intriguing Fe-based Raman features as well as structural subtleties in LaFeSiH suggesting that this superconductor may formally be non-centrosymmetric., Comment: 7 pages, 4 figures

Understanding the polarization switching mechanisms at play in ferroelectric materials is crucial for their exploitation in electronic devices. The conventional centrosymmetric reference structure-based mechanism which accounts for ferroelectricity in most of the usual displacive ferroelectric materials is too energy-demanding for some newly diagnosed ferroelectric materials such as the Ga2-xFexO3 (0.8 < x < 1.4) compounds. Some alternative theoretical propositions have been made and need experimental confirmation. A dual-scale electron microscopy study is performed on thin films of the Ga0.6Fe1.4O3 multiferroic compound. A wide scale precession-assisted electron diffraction tomography study first allows the determination of the structure the compound adopts in thin films, and even permits the refinement of the atomic positions within this structure. Cationic mobility is suggested for two of the atomic positions through the existence of extra electronic density. A local in situ high resolution scanning transmission electron microscopy study then allows confirming these mobilities by directly spotting the cationic displacements on successively acquired images. The whole study confirms an unconventional switching mechanism via local domain wall motion in this compound.

High entropy alloys (HEAs) are the new class of materials with an attractive combination of tunable mechanical and physicochemical properties. They crystallize mainly in cubic structures, however, for practical applications, HEAs with hexagonal close-packed (hcp) structure are highly desirable in connection to their in general high hardness. Herein, we report the synthesis, structure and detailed superconducting properties of Re$_{0.56}$Nb$_{0.11}$Ti$_{0.11}$Zr$_{0.11}$Hf$_{0.11}$-the first hexagonal superconducting high entropy alloy (HEA) composed of five randomly distributed transition-metals. Combination of room temperature precession electron diffraction, precession electron diffraction tomography and powder X-ray diffraction is utilized to determine the room temperature crystal structure. Transport, magnetic and heat capacity measurements show that the material is a type-II superconductor with the bulk superconducting transition at $T_{c}$ = 4.4 K, lower critical field $H_{c1}$(0) = 2.3 mT and upper critical field $H_{c2}$(0) = 3.6 T. Low-temperature specific heat measurement indicates that Re$_{0.56}$Nb$_{0.11}$Ti$_{0.11}$Zr$_{0.11}$Hf$_{0.11}$ is a phonon-mediated superconductor in the weak electron-phonon coupling limit with a normalized specific heat jump $\frac{\Delta C_{el}}{\gamma_{n}T_{c}}$ = 1.32. Further, hexagonal to cubic structural transition is observed by lowering the valence electron counts and $T_{c}$ follows crystalline-like behaviour., Comment: 6 Pages, 9 Figures. arXiv admin note: text overlap with arXiv:1804.10092

We study the transport properties in SrVO3/LaVO3 (SVO/LVO) superlattices deposited on SrTiO3 (STO) substrates. We show that the electronic conduction occurs in the metallic LVO layers with a galvanomagnetism typical of a 2D Fermi surface. In addition, a Kondo-like component appears in both the thermal variation of resistivity and the magnetoresistance. Surprisingly, in this system where the STO interface does not contribute to the measured conduction, the Kondo correction is strongly anisotropic. We show that the growth temperature allows a direct control of this contribution. Finally, the key role of vanadium mixed valency stabilized by oxygen vacancies is enlightened., Comment: Accepted In Journal of Physics: Cond Mat. Supp Mat File included

A series of 100 nm LaVO3 thin films have been synthesized on (001)-oriented SrTiO3 substrates using the pulsed laser deposition technique, and the effects of growth temperature are analyzed. Transport properties reveal a large electronic mobility and a non-linear Hall effect at low temperature. In addition, a cross-over from a semiconducting state at high-temperature to a metallic state at low-temperature is observed, with a clear enhancement of the metallic character as the growth temperature increases. Optical absorption measurements combined with the two-bands analysis of the Hall effect show that the metallicity is induced by the diffusion of oxygen vacancies in the SrTiO3 substrate. These results allow to understand that the film/substrate heterostructure behaves as an original semiconducting-metallic parallel resistor, and electronic transport properties are consistently explained., Comment: Improved version as accepted in Journ Phys: Cond Mat. Additional Optical measurements are presented

Rare earth perovskite oxides constitute a wide family of materials presenting functional proper- ties strongly coupled to their crystalline structure. Here, we report on the experimental results on epitaxial PrVO3 deposited on SrTiO3 single crystal substrates by pulsed laser deposition. By com- bining advanced structural characterization tools, we have observed that the PVO unrelaxed film structure grown on STO, is characterized by two kinds of oriented domains whose epitaxial relations are: (i) PrVO3[110]o//SrTiO3[001]c and PrVO3[001]o//SrTiO3[100]c, (ii) PrVO3[110]o//SrTiO3[001]c and PrVO3[001]o//SrTiO3[010]c. We have also measured reciprocal space maps. From these results, we have determined that the PVO film epitaxy on STO imposes a lowering of the PVO structure symmetry from orthorhombic (Pbnm) to monoclinic (P21/m). We show, the nominal strain induced by the substrate being constant, that the obtained film structure depends on both growth oxygen and temperature. Thus, by finely controlling the deposition conditions, we could tune the strain experienced by PrVO3 thin film. These results show an alternative to substrate mismatch as a path to control the strain and structure of PVO films.

While structure refinement is routinely achieved for simple bulk materials, the accurate structural determination still poses challenges for thin films due on the one hand to the small amount of material deposited on the thicker substrate and, on the other hand, to the intricate epitaxial relationships that substantially complicate standard X-ray diffraction analysis. Using a combined approach, we analyze the crystal structure of epitaxial LaVO$_3$ thin films grown on (100)-oriented SrTiO$_3$. Transmission electron microscopy study reveals that the thin films are epitaxially grown on SrTiO$_3$ and points to the presence of 90$^{\circ}$ oriented domains. The mapping of the reciprocal space obtained by high resolution X-ray diffraction permits refinement of the lattice parameters. We finally deduce that strain accommodation imposes a monoclinic structure onto the LaVO$_3$ film. The reciprocal space maps are numerically processed and the extracted data computed to refine the atomic positions, which are compared to those obtained using precession electron diffraction tomography. We discuss the obtained results and our methodological approach as a promising thin film structure determination for complex systems., Comment: 8 pages, 6 figures, 4 tables

A \ce{(LaVO_3)_6/(SrVO_3)_3} superlattice is studied with a combination of sub-{\AA} resolved scanning transmission electron microscopy and monochromated electron energy-loss spectroscopy. The V oxidation state is mapped with atomic spatial resolution enabling to investigate electronic reconstruction at the \ce{LaVO_3}/\ce{SrVO_3} interfaces. Surprisingly, asymmetric charge distribution is found at adjacent chemically symmetric interfaces. The local structure is proposed and simulated with double channeling calculation which agrees qualitatively with our experiment. We demonstrate that local strain asymmetry is the likely cause of the electronic asymmetry of the interfaces. The electronic reconstruction at the interfaces extends much further than the chemical composition, varying from 0.5 to 1.2 nm. This distance corresponds to the length of charge transfer previously found in the \ce{(LaVO_3)_m}/\ce{(SrVO_3)_n} metal/insulating and the \ce{(LaAlO_3)_m}/\ce{(SrTiO_3)_n} insulating/insulating interfaces., Comment: 6 pages, 5 figures. Physical Review B, 2013

Epitaxial CaMnO3 films grown with 2.3% tensile strain on (001)-oriented LaAlO3 substrates are found to be incipiently ferroelectric below 25 K. Optical second harmonic generation (SHG) was used for the detection of the incipient polarization. The SHG analysis reveals that CaMnO3 crystallites with in-plane orientation of the orthorhombic b axis contribute to an electric polarization oriented along the orthorhombic a (resp.\ c) axis in agreement with the predictions from density functional calculations.

Measurements of the resistive properties and the lattice parameters of a (LaVO3)[6 unit cells]/(SrVO3)[1 unit cell] superlattice between 10K and room temperature are presented. A low temperature metallic phase compatible with a Fermi liquid behavior is evidenced. It disappears in the vicinity of a structural transition from a monoclinic to tetragonal phase, in which disorder seems to strongly influence the transport. Our results will enrich the understanding of the electronic properties of complex heterostructures., Comment: accepted in APL 2011

The structure and interface characteristics of (LaVO3)6m(SrVO3)m superlattices deposited on (100)-SrTiO3 (STO) substrate were studied using Transmission Electron Microscopy (TEM). Cross-section TEM studies revealed that both LaVO3 (LVO) and SrVO3 (SVO) layers are good single crystal quality and epitaxially grown with respect to the substrate. It is evidenced that LVO layers are made of two orientational variants of a distorted perovskite compatible with bulk LaVO3 while SVO layers suffers from a tetragonal distortion due to the substrate induced stain. Electron Energy Loss Spectroscopy (EELS) investigations indicate changes in the fine structure of the V L23 edge, related to a valence change between the LaVO3 and SrVO3 layers., Comment: submitted for publication in PRB

We have measured the magnetic properties of a mixed valency iron phosphate. It presents an original structure with crossed chains containing Fe II and orthogonal to the longest direction of the crystallites. Microstructural investigations using electron microscopy show the presence of random nano-twinning. The ac susceptibility measurements demonstrate similarities with the kinetics of a disordered magnetic, spin-glass like, state but are shown to be essentially due to this peculiar disorder. Scaling properties are characteristics of 3D second order transition implying that this disorder at a small scale does not influence significantly long range magnetic ordering. At low temperature, a decrease of the spontaneous magnetization and an irreversible metamagnetic transition is observed, and is attributed to a canting of the spins in the iron chain., Comment: accepted for publication in PRB

We report on a systematic study of a number of structurally identical but chemically distinct transition metal oxides in order to determine how the material-specific properties such as the composition and the strain affect the properties at the interface of heterostructures. Our study considers a series of structures containing two layers of ferromagnetic SrRuO3, with antiferromagnetic insulating manganites sandwiched in between. The results demonstrate how to control the strength and relative orientation of interfacial ferromagnetism in correlated electron materials by means of valence state variation and substrate-induced strain, respectively.

The structure and microstrucutre of fully-strained BiCrO3 thin films have been investigated by X-rays diffraction and transmission electron microscopy, at room temperature. Interestingly, three structural variants are simultaneously stabilized within the film. While txo of them are consistent with the existing phases in the bulk-below and above the 420 K structural transition, a different phase is identified. The existence of various structures has been attributed to the inhomogeneous distribution of local strains and oxygens resulting from a minimization of the strain-energy at the interface. These findings will open the route to a better understanding of Bi-based perovskites and metastable phases., Comment: 10 pages, 5 figures, to be published in Applied Physics Letters

Ferroelectric domains were investigated using piezoresponse force microscopy in superlattices composed of multiferroic BiFeO3 and SrTiO3 layers. Compared to single BiFeO3 thin films, a reduction in the domains size and a suppression of the in-plane orientation of domains are observed in a superlattice of (BiFeO3)4(SrTiO3)8, suggesting a constrained ferroelectric domain orientation along the out-of-plane <001> direction. Such modification of domain size and orientation in BiFeO3-based heterostructures could play a vital role on engineering the domains and domain wall mediated functional properties necessary for device applications, Comment: 12 pages, 4 figures, To be published in APL

Calcium cobaltite thin films with a ratio Ca/Co=1 were grown on (101)-NdGaO3 substrate by the pulsed laser deposition technique. The structure of the deposited metastable phase is solved using a precession electron diffraction 3D dataset recorded from a cross-sectional sample. It is shown that an ordered oxygen-deficient Ca2Co2O5+d perovskite of the brownmillerite-type with lattice parameters a= 0.546nm, b=1.488nm and c=0.546nm (SG: Ibm2) has been stabilized using the substrate induced strain. The structure and microstructure of this metastable cobaltite is further discussed and compared to related bulk materials based on our transmission electron microscopy investigations, Comment: 13 pages, 10 figures, 2 tables, accepted in Phys. Rev. B

The synthesis and structural study of the stoichiometric perovskite La0.5Ba0.5CoO3 have allowed three forms to be isolated. Besides the disordered La0.5Ba0.5CoO3 and the perfectly ordered layered LaBaCo2O6, a third form called nanoscale-ordered LaBaCo2O6, is obtained. As evidenced by transmission electron microscopy investigations, the latter consists of 112-type 90 degree oriented domains fitted into each other at a nanometer scale which induce large strains and consequently local atomic scale lattice distortions. These three ferromagnetic perovskites exhibit practically the same Tc (174-179 K), but differently from the other phases, the nanoscale-ordered LaBaCo2O6 is a hard ferromagnet, with Hc = 4.2 kOe, due to the strains which may pin domain walls, preventing the reversal of the spins in a magnetic field. The magnetotransport properties of these phases show that all of them exhibit a maximum intrinsic magnetoresistance, close to 6-7 % around Tc under 70 kOe but that the ordered phase exhibits a much higher tunnelling magnetoresistance effect at low temperature of about 15 % against 4 % due to the grain boundary effects., Comment: 26 pages, higher resolution figs (will be@chem. mat.2008)

The electronic transport properties and the magnetic susceptibility were measured in detail in $YBaCo_2O_{5.45}$. Close to the so-called metal-insulator transition, strong effects of resistance relaxation, a clear thermal hysteresis and a sudden increase of the resistance noise are observed. This is likely due to the first order character of the transition and to the underlying phases coexistence. Despite these out of equilibrium features, a positive and linear magneto-resistance is also observed, possibly linked to the heterogeneity of the state. From a magnetic point of view, the paramagnetic to ordered magnetic state transition is observed using non linear susceptibilty. This transition shows the characteristics of a continuous transition, and time dependent effects can be linked with the dynamics of magnetic domains in presence of disorder. Thus, when focusing on the order of the transitions, the electronic one and the magnetic one can not be directly associated., Comment: accepted for publication in PRB

A new nanoscale ordered perovskite cobaltite, which consists of 90 degree ordered domains of the layered-112 LaBaCo2O6 has been evidenced by high resolution- transmission electron microscopy. This new form, like the disordered La0.5Ba0.5CoO3 and ordered LaBaCo2O6, exhibits a ferromagnetic transition at TC around 179 K. However, it differs from the two previous forms by its strong magnetic anisotropy, and correlatively by its high value of coercivity (0.42 Tesla) at low temperature. We suggest that this behaviour originates from the locking of magnetic spins in the 90 degree oriented nano-domain. Moreover, one observes a semi-metal/semi-metal transition at TC with a maximum magnetoresistance of 6.5 % at this temperature., Comment: 16 pages including figures

Epitaxial La2NiMnO6 thin films have been grown on (001)-oriented SrTiO3 using the PLD technique. The thin films are semiconducting and FM with a TC close to 270K, a coercive field of 920Oe, and a saturation magnetization of 5muB per f.u. TEM, conducted at RT, reveals a majority phase having "I-centered" structure with a=c=1.4asub and b=2asub along with a minority phase-domains having "P-type" structure (asub being the lattice parameter of the perovskite structure). A discusion on the presence of Ni/Mn long-range ordering, in light of recent literature on double perovskites La2NiMnO6 is presented., Comment: To be published in Applied Physics Letters