Ab Initio Phase Diagram of Gold in Extreme Conditions.

A phase diagram of gold is proposed in the [0; 1000] GPa and [0; 10 000] K ranges of pressure and temperature, respectively, topologically modified with respect to previous predictions. Using finite-temperature ab initio simulations and nonequilibirum thermodynamic integration, both accelerated by machine learning, we evaluate the Gibbs free energies of three solid phases previously proposed. At room temperature, the face-centered cubic (fcc) phase is stable up to ∼500 GPa whereas the body-centered cubic (bcc) phase only appears above 1 TPa. At higher temperature, we do not highlight any fcc-bcc transition line between 200 and 400 GPa, in agreement with ramp-compressed experiments. The present results only disclose a bcc domain around 140-235 GPa and 6000-8000 K, consistent with the triple point recently found in shock experiments. We demonstrate that this re-stabilization of the bcc phase at high temperature is due to anharmonic effects.

Machine learning accelerated random structure searching: Application to yttrium superhydrides.

The search for new superhydrides, promising materials for both hydrogen storage and high temperature superconductivity, made great progress, thanks to atomistic simulations and Crystal Structure Prediction (CSP) algorithms. When they are combined with Density Functional Theory (DFT), these methods are highly reliable and often match a great part of the experimental results. However, systems of increasing complexity (number of atoms and chemical species) become rapidly challenging as the number of minima to explore grows exponentially with the number of degrees of freedom in the simulation cell. An efficient sampling strategy preserving a sustainable computational cost then remains to be found. We propose such a strategy based on an active-learning process where machine learning potentials and DFT simulations are jointly used, opening the way to the discovery of complex structures. As a proof of concept, this method is applied to the exploration of tin crystal structures under various pressures. We showed that the α phase, not included in the learning process, is correctly retrieved, despite its singular nature of bonding. Moreover, all the expected phases are correctly predicted under pressure (20 and 100 GPa), suggesting the high transferability of our approach. The method has then been applied to the search of yttrium superhydrides (YHx) crystal structures under pressure. The YH6 structure of space group Im-3m is successfully retrieved. However, the exploration of more complex systems leads to the appearance of a large number of structures. The selection of the relevant ones to be included in the active learning process is performed through the analysis of atomic environments and the clustering algorithm. Finally, a metric involving a distance based on x-ray spectra is introduced, which guides the structural search toward experimentally relevant structures. The global process (active-learning and new selection methods) is finally considered to explore more complex and unknown YHx phases, unreachable by former CSP algorithms. New complex phases are found, demonstrating the ability of our approach to push back the exponential wall of complexity related to CSP.

Hexagonal Layered Polymeric Nitrogen Phase Synthesized near 250 GPa.

The nitrogen triple bond dissociates in the 100 GPa pressure range and a rich variety of single-bonded polymeric nitrogen structures unique to this element have been predicted up to the terapascal pressure range. The nonmolecular cubic-gauche (cg-N) structure was first observed above 110 GPa, coupled to high temperature (>2000 K) to overcome the kinetic barrier. A mixture of cg-N with a layered phase was afterwards reported between 120 and 180 GPa. Here, by laser heating pure nitrogen from 180 GPa, a sole crystalline phase is characterized above 240 GPa while an amorphous transparent phase is obtained at pressures below. X-ray diffraction and Raman vibrational data reveal a tetragonal lattice (P4_{2}bc) that matches the predicted hexagonal layered polymeric nitrogen (HLP-N) structure. Density-functional theory calculations which include the thermal and dispersive interaction contributions are performed to discuss the stability of the HLP-N structure.

Polarization sensitive surface band structure of doped BaTiO3(001).

We present a spatial and wave-vector resolved study of the electronic structure of micron sized ferroelectric domains at the surface of a BaTiO(3)(001) single crystal. The n-type doping of the BaTiO(3) is controlled by in situ vacuum and oxygen annealing, providing experimental evidence of a surface paraelectric-ferroelectric transition below a critical doping level. Real space imaging of photoemission threshold, core level and valence band spectra show contrast due to domain polarization. Reciprocal space imaging of the electronic structure using linearly polarized light provides unambiguous evidence for the presence of both in- and out-of-plane polarization with two- and fourfold symmetry, respectively. The results agree well with first principles calculations.

BiFeO3 films under tensile epitaxial strain from first principles.

Density-functional calculations are performed to predict structural and magnetic properties of (001) BiFeO(3) films under tensile epitaxial strain. These films remain monoclinic (Cc space group) for misfit strains between 0% and ≈8%, with the polarization, tilt axis and magnetization all rotating when varying the strain. At a tensile strain ≈8%, these films undergo a first-order phase transition towards an orthorhombic phase (Ima2 space group). In this novel phase, the polarization and tilt axis lie in the epitaxial plane, while the magnetization is along the out-of-plane direction and the direction of the antiferromagnetic vector is unchanged by the phase transition. An unexpected additional degree of freedom, namely, an antiphase arrangement of Bi atoms, is also found for all tensile strains.

Multiferroic phase transition near room temperature in BiFeO3 films.

In multiferroic BiFeO(3) thin films grown on highly mismatched LaAlO(3) substrates, we reveal the coexistence of two differently distorted polymorphs that leads to striking features in the temperature dependence of the structural and multiferroic properties. Notably, the highly distorted phase quasiconcomitantly presents an abrupt structural change, transforms from a standard to a nonconventional ferroelectric, and transitions from antiferromagnetic to paramagnetic at 360±20 K. These coupled ferroic transitions just above room temperature hold promises of giant piezoelectric, magnetoelectric, and piezomagnetic responses, with potential in many applications fields.

Low-symmetry phases in ferroelectric nanowires.

Ferroelectric nanostructures have recently attracted much attention due to the quest of miniaturizing devices and discovering novel phenomena. In particular, studies conducted on two-dimensional and zero-dimensional ferroelectrics have revealed original properties and their dependences on mechanical and electrical boundary conditions. Meanwhile, researches aimed at discovering and understanding properties of one-dimensional ferroelectric nanostructures are scarce. The determination of the structural phase and of the direction of the polarization in one-dimensional ferroelectrics is of technological importance, since, e.g., a low-symmetry phase in which the polarization lies away from a highly symmetric direction typically generates phenomenal dielectric and electromechanical responses. Here, we investigate the phase transition sequence of nanowires made of KNbO(3) and BaTiO(3) perovskites, by combining X-ray diffraction, Raman spectroscopy, and first-principles-based calculations. We provide evidence of a previously unreported ferroelectric ground state of monoclinic symmetry and the tuning of the polarization's direction by varying factors inherent to the nanoscale.

Bridging multiferroic phase transitions by epitaxial strain in BiFeO3.

We report the influence of epitaxial strain on the multiferroic phase transitions of BiFeO3 films. Using advanced characterization techniques and calculations we show that while the magnetic Néel temperature hardly varies, the ferroelectric Curie temperature TC decreases dramatically with strain. This is in contrast with the behavior of standard ferroelectrics where strain enhances the polar cation shifts and thus TC. We argue that this is caused by an interplay of polar and oxygen tilting instabilities and that strain can drive both transitions close together to yield increased magnetoelectric responses.

Synthesis of FeH5: A layered structure with atomic hydrogen slabs.

High pressure promotes the formation of polyhydrides with unusually high hydrogen-to-metal ratios. These polyhydrides have complex hydrogenic sublattices. We synthesized iron pentahydride (FeH5) by a direct reaction between iron and H2 above 130 gigapascals in a laser-heated diamond anvil cell. FeH5 exhibits a structure built of atomic hydrogen only. It consists of intercalated layers of quasicubic FeH3 units and four-plane slabs of thin atomic hydrogen. The distribution of the valence electron density indicates a bonding between hydrogen and iron atoms but none between hydrogen atoms, presenting a two-dimensional metallic character. The discovery of FeH5 suggests a low-pressure path to make materials that approach bulk dense atomic hydrogen.

Two-level lumbar total disc replacement: functional outcomes and segmental motion after 4 years.

INTRODUCTION: Lumbar total disc replacement is an effective treatment for single-level discogenic lower back pain. But the replacement of two disc levels is controversial. HYPOTHESIS: Two-level total disc replacement will improve function while preserving spinal motion. MATERIAL AND METHODS: A continuous series of 108 patients (51 women, 57 men) surgically treated over two levels with the ProDisc-L implant (Synthes Spine) was evaluated retrospectively with an average follow-up of 4 years. Ninety-three of these patients were operated for L4/L5 and L5/S1 degenerative disc disease, while 15 were operated for L3/L4 and L4/L5 disease. The procedure was carried out through the left retroperitoneal approach in 65 patients, the right retroperitoneal approach in 42 patients and both approaches in 1 patient. The Oswestry score, lumbar VAS and radicular VAS were used to evaluate function. The motion of the prosthetic disc segments was evaluated using Cobb's method. Data were collected prospectively in the context of regular patient monitoring. A retrospective analysis was carried out by an independent examiner. RESULTS: The procedure led to a statistically significant improvement in the functional scores. The motion of the upper disc segment was 9° (0°-19°) in flexion/extension and 5.5° (2°-12°) in lateral bending. It was 6.2° (0°-14°) and 1.9° (0°-7°) at the lower disc segment. The range of motion was similar in L3/L4 and L4/L5, but was less in L5/S1. Lack of mobility was not correlated with alterations in the functional outcome. The complication rate was 18%. DISCUSSION: Two-level lumbar disc replacement improves spinal function while preserving its mobility. But this procedure is fraught with risks and must be carried out by a highly-experienced team. A longer follow-up is needed to evaluate the sustainability of the results and to detect any adjacent segment disease. The French National Authority for Health (HAS) has recommended against two-level lumbar disc replacement, so it no longer can be performed in France.

Strain dependence of polarization and piezoelectric response in epitaxial BiFeO3 thin films.

Epitaxial strain has recently emerged as a powerful means to engineer the properties of ferroelectric thin films, for instance to enhance the ferroelectric Curie temperature (T(C)) in BaTiO(3). However, in multiferroic BiFeO(3) thin films an unanticipated strain-driven decrease of T(C) was reported and ascribed to the peculiar competition between polar and antiferrodistortive instabilities. Here, we report a systematic characterization of the room-temperature ferroelectric and piezoelectric properties for strain levels ranging between -2.5% and +1%. We find that polarization and the piezoelectric coefficient increase by about 20% and 250%, respectively, in this strain range. These trends are well reproduced by first-principles-based techniques.

Evidence for room-temperature multiferroicity in a compound with a giant axial ratio.

In the search for multiferroic materials magnetic compounds with a strongly elongated unit-cell (large axial ratio c/a) have been scrutinized intensely. However, none was hitherto proven to have a switchable polarization, an essential feature of ferroelectrics. Here, we provide evidence for the epitaxial stabilization of a monoclinic phase of BiFeO3 with a giant axial ratio (c/a=1.23) that is both ferroelectric and magnetic at room temperature. Surprisingly, and in contrast with previous theoretical predictions, the polarization does not increase dramatically with c/a. We discuss our results in terms of the competition between polar and antiferrodistortive instabilities and give perspectives for engineering multiferroic phases.