Stability of the tetragonal phase of BaZrO3 under high pressure

in PHYSICAL REVIEW B (2022), 106(6), 064105-10

In this paper, we revisit the high pressure behavior of BaZrO3 by a combination of first-principle calculations, Raman spectroscopy and x-ray diffraction under high pressure. We confirm experimentally the ... [more ▼]

In this paper, we revisit the high pressure behavior of BaZrO3 by a combination of first-principle calculations, Raman spectroscopy and x-ray diffraction under high pressure. We confirm experimentally the cubic-to -tetragonal transition at 10 GPa and find no evidence for any other phase transition up to 45 GPa, the highest pressures investigated, at variance with past reports. We reinvestigate phase stability with density functional theory considering not only the known tetragonal (I4/mcm) phase but also other potential antiferrodistortive candidates. This shows that the tetragonal phase becomes progressively more stable upon increasing pressure as compared to phases with more complex tilt systems. The possibility for a second transition to another tilted phase at higher pressures, and in particular to the very common orthorhombic Pnma structure, is therefore ruled out. [less ▲]

Emerging spin-phonon coupling through cross-talk of two magnetic sublattices

in NATURE COMMUNICATIONS (2022), 13(1), 443-7

Typically, magnetic phenomena result from the spontaneous order of the sublattices. Here, the cross-talk of two magnetic ions gives rise to an intrinsic, yet non-spontaneous ordering and manifests as ... [more ▼]

Typically, magnetic phenomena result from the spontaneous order of the sublattices. Here, the cross-talk of two magnetic ions gives rise to an intrinsic, yet non-spontaneous ordering and manifests as emergent strong spin-phonon coupling in SmFeO3. Many material properties such as superconductivity, magnetoresistance or magnetoelectricity emerge from the non-linear interactions of spins and lattice/phonons. Hence, an in-depth understanding of spin-phonon coupling is at the heart of these properties. While most examples deal with one magnetic lattice only, the simultaneous presence of multiple magnetic orderings yield potentially unknown properties. We demonstrate a strong spin-phonon coupling in SmFeO3 that emerges from the interaction of both, iron and samarium spins. We probe this coupling as a remarkably large shift of phonon frequencies and the appearance of new phonons. The spin-phonon coupling is absent for the magnetic ordering of iron alone but emerges with the additional ordering of the samarium spins. Intriguingly, this ordering is not spontaneous but induced by the iron magnetism. Our findings show an emergent phenomenon from the non-linear interaction by multiple orders, which do not need to occur spontaneously. This allows for a conceptually different approach in the search for yet unknown properties. [less ▲]

Crossover between distinct symmetries in solid solutions of rare earth nickelates

in APL MATERIALS (2021), 9(8),

A strong coupling of the lattice to functional properties is observed in many transition metal oxide systems, such as the ABO(3) perovskites. In the quest for tailor-made materials, it is essential to be ... [more ▼]

A strong coupling of the lattice to functional properties is observed in many transition metal oxide systems, such as the ABO(3) perovskites. In the quest for tailor-made materials, it is essential to be able to control the structural properties of the compound(s) of interest. Here thin film solid solutions that combine NdNiO3 and LaNiO3, two materials with the perovskite structure but distinct space groups, are analyzed. Raman spectroscopy and scanning transmission electron microscopy are combined in a synergistic approach to fully determine the mechanism of the structural crossover with chemical composition. It is found that the symmetry transition is achieved by phase coexistence in a way that depends on the substrate selected. These results carry implications for analog-tuning of physical properties in future functional materials based on these compounds. [less ▲]

Vibrational properties of LaNiO3 films in the ultrathin regime

in APL MATERIALS (2020), 8(6),

Collective rotations and tilts of oxygen polyhedra play a crucial role in the physical properties of complex oxides such as magnetism and conductivity. Such rotations can be tuned by preparing thin films ... [more ▼]

Collective rotations and tilts of oxygen polyhedra play a crucial role in the physical properties of complex oxides such as magnetism and conductivity. Such rotations can be tuned by preparing thin films in which dimensionality, strain, and interface effects come into play. However, little is known of the tilt and rotational distortions in films a few unit cells thick including the question of if coherent tilt patterns survive at all in this ultrathin limit. Here, a series of films of perovskite LaNiO3 is studied and it is shown that the phonon mode related to oxygen octahedral tilts can be followed by Raman spectroscopy down to a film thickness of three pseudocubic perovskite unit cells (similar to 1.2 nm). To push the limits of resolution to the ultrathin regime, a statistical analysis method is introduced to separate the Raman signals of the film and substrate. Most interestingly, these analyses reveal a pronounced hardening of the tilt vibrational mode in the thinnest films. A comparison between the experimental results, first principles simulations of the atomic structure, and the standing wave model, which accounts for size effects on the phononic properties, reveals that in the ultrathin regime, the Raman spectra are a hybrid entity of both the bulk and surface phononic behavior. These results showcase Raman spectroscopy as a powerful tool to probe the behavior of perovskite films down to the ultrathin limit. [less ▲]

Role of the ferroelastic strain in the optical absorption of BiVO4

in APL MATERIALS (2020), 8(8),

Bismuth vanadate (BiVO4) has recently been under focus for its potential use in photocatalysis thanks to its well-suited absorption edge in the visible light range. Here, we characterize the optical ... [more ▼]

Bismuth vanadate (BiVO4) has recently been under focus for its potential use in photocatalysis thanks to its well-suited absorption edge in the visible light range. Here, we characterize the optical absorption of a BiVO4 single crystal as a function of temperature and polarization direction by reflectance and transmittance spectroscopy. The optical bandgap is found to be very sensitive to the temperature, and to the tetragonal-to-monoclinic ferroelastic transition at 523 K. The anisotropy, as measured by the difference in the absorption edge for the light polarized parallel and perpendicular to the principal axis, is reduced from 0.2 eV in the high-temperature tetragonal phase to 0.1 eV at ambient temperature. We show that this evolution is dominantly controlled by the ferroelastic shear strain. These findings provide a route for further optimization of bismuth vanadate-based light absorbers in photocatalytic devices. [less ▲]

Accelerated Ionic Motion in Amorphous Memristor Oxides for Nonvolatile Memories and Neuromorphic Computing

in ADVANCED FUNCTIONAL MATERIALS (2019), 29(5),

Memristive devices based on mixed ionic-electronic resistive switches have an enormous potential to replace today's transistor-based memories and Von Neumann computing architectures thanks to their ... [more ▼]

Memristive devices based on mixed ionic-electronic resistive switches have an enormous potential to replace today's transistor-based memories and Von Neumann computing architectures thanks to their ability for nonvolatile information storage and neuromorphic computing. It still remains unclear however how ionic carriers are propagated in amorphous oxide films at high local electric fields. By using memristive model devices based on LaFeO3 with either amorphous or epitaxial nanostructures, we engineer the structural local bonding units and increase the oxygen-ionic diffusion coefficient by one order of magnitude for the amorphous oxide, affecting the resistive switching operation. We show that only devices based on amorphous LaFeO3 films reveal memristive behavior due to their increased oxygen vacancy concentration. We achieved stable resistive switching with switching times down to microseconds and confirm that it is predominantly the oxygen-ionic diffusion character and not electronic defect state changes that modulate the resistive switching device response. Ultimately, these results show that the local arrangement of structural bonding units in amorphous perovskite films at room temperature can be used to largely tune the oxygen vacancy (defect) kinetics for resistive switches (memristors) that are both theoretically challenging to predict and promising for future memory and neuromorphic computing applications. [less ▲]

Optical spectroscopy on the photo-response in multiferroic BiFeO3 at high pressure

in JOURNAL OF APPLIED PHYSICS (2019), 126(16),

The pressure dependence of light-induced effects in single-crystalline BiFeO3 is studied by optical spectroscopy. At low pressures, we observe three light-induced absorption features with energies just ... [more ▼]

The pressure dependence of light-induced effects in single-crystalline BiFeO3 is studied by optical spectroscopy. At low pressures, we observe three light-induced absorption features with energies just below the two crystal-field excitations and the absorption onset, respectively. These absorption features were previously ascribed to excitons, possibly connected with the ultrafast photostriction effect in BiFeO3. The pressure-induced redshift of the absorption features follows the pressure dependence of the corresponding crystal-field excitations and absorption onset, suggesting the link between them. Above the structural phase transition at P-c1 approximate to 3.5 GPa, the three absorption features disappear, suggesting their connection to the polar phase in BiFeO3. The pressure-induced disappearance of the photoinduced features is irreversible upon pressure release. Published under license by AIP Publishing. [less ▲]

Temperature-dependent photo-response in multiferroic BiFeO3 revealed by transmission measurements

in JOURNAL OF APPLIED PHYSICS (2019), 125(11),

We studied the light-induced effects in BiFeO3 single crystals as a function of temperature by means of optical spectroscopy. Here, we report the observation of several light-induced absorption features ... [more ▼]

We studied the light-induced effects in BiFeO3 single crystals as a function of temperature by means of optical spectroscopy. Here, we report the observation of several light-induced absorption features which are discussed in terms of the photostriction effect and are interpreted in terms of excitons. The temperature dependence of their energy position suggests a possible coupling between the excitons and the lattice vibrations. Moreover, there are hints for anomalies in the temperature evolution of the excitonic features, which might be related to the temperature-induced magnetic phase transitions in BiFeO3. Our findings suggest a coupling between light-induced excitons and the lattice and spin degrees of freedom, which might be relevant for the observed ultrafast photostriction effect in multiferroic BiFeO3. Published under license by AIP Publishing. [less ▲]

Rare-earth nickelates RNiO3: thin films and heterostructures

in REPORTS ON PROGRESS IN PHYSICS (2018), 81(4),

This review stands in the larger framework of functional materials by focussing on heterostructures of rare-earth nickelates, described by the La, Pr, Nd Sm,., Lu. Nickelates are characterized by a rich ... [more ▼]

This review stands in the larger framework of functional materials by focussing on heterostructures of rare-earth nickelates, described by the La, Pr, Nd Sm,., Lu. Nickelates are characterized by a rich phase diagram of structural and physical properties and serve as a benchmark for the physics of phase transitions in correlated oxides where electron-lattice coupling plays a key role. Much of the recent interest in nickelates concerns heterostructures, that is single layers of thin film multilayers or superlattices, with the general objective of modulating their physical properties through strain control, confinement or interface effects. We will discuss the extensive studies on nickelate heterostructures as well as outline different approaches to tuning and controlling their physical properties and, finally, review application concepts for future devices. [less ▲]

Raman signatures of ferroic domain walls captured by principal component analysis

in Journal of Physics: Condensed Matter (2018), 30(3),

Ferroic domain walls are currently investigated by several state-of-the art techniques in order to get a better understanding of their distinct functional properties. Here, principal component analysis ... [more ▼]

Ferroic domain walls are currently investigated by several state-of-the art techniques in order to get a better understanding of their distinct functional properties. Here, principal component analysis (PCA) of Raman maps is used to study ferroelectric domain walls (DWs) in LiNbO3 and ferroelastic DWs in NdGaO3. It is shown that PCA allows us to quickly and reliably identify small Raman peak variations at ferroelectric DWs and that the value of a peak shift can be deduced-accurately and without a priori-from a first order Taylor expansion of the spectra. The ability of PCA to separate the contribution of ferroelastic domains and DWs to Raman spectra is emphasized. More generally, our results provide a novel route for the statistical analysis of any property mapped across a DW. [less ▲]