Marios Hadjimichael

This work focuses on the complex ferroelastic/ferroelectric domain structure in the prototypical ferroelectric PbTiO3 epitaxially strained on (110)o-oriented DyScO3 substrates, with a 22 nm-thick bottom SrRuO3 electrode. High quality epitaxial growth has been achieved from 7.2 nm (18 unit cells) up to 288 nm (720 unit cells) PbTiO3 film thickness. The evolution of the domain configuration and its scaling with the PbTiO3 film thickness are studied using a combination of atomic force microscopy, x-ray diffraction, piezoresponse force microscopy, and high resolution scanning transmission electron microscopy. A large asymmetry in the domain configuration is found due to the anisotropic strain imposed by the orthorhombic substrate. For thicker films, a larger scale arrangement of domains into superdomains is observed, with size that scales with the PbTiO3 film thickness, allowing a fine-tuning of their density. These superdomain structures affect the functional properties of the ferroelectric material and may play a role in switching devices such as memories. The presence of superdomains implies the existence of superdomain walls, which potentially exhibit properties intrinsically different from those of conventional ferroelastic or ferroelectric domain walls, opening the possibility of a new kind of superdomain wall-based nanoelectronics.

The observation of unexpected polarization textures such as vortices, skyrmions, and merons in various oxide heterostructures has challenged the widely accepted picture of ferroelectric domain walls as being Ising-like. Bloch components in the 180° domain walls of PbTiO 3 have recently been reported in PbTiO 3 / SrTiO 3 superlattices and linked to domain wall chirality. While this opens exciting perspectives, the ubiquity of this Bloch component remains to be further explored. In this work, we present a comprehensive investigation of domain walls in PbTiO 3 / SrTiO 3 superlattices, involving a combination of first- and second-principles calculations, phase-field simulations, diffuse scattering calculations, and synchrotron-based diffuse x-ray scattering. Our theoretical calculations highlight that the previously predicted Bloch polarization in the 180° domain walls in PbTiO 3 / SrTiO 3 superlattices might be more sensitive to the boundary conditions than initially thought and is not always expected to appear. Employing diffuse scattering calculations for larger systems, we develop a method to probe the complex structure of domain walls in these superlattices via diffuse x-ray scattering measurements. Through this approach, we investigate depolarization-driven ferroelectric polarization rotation at the domain walls. Our experimental findings, consistent with our theoretical predictions for realistic domain periods, do not reveal any signatures of a Bloch component in the centers of the 180° domain walls of PbTiO 3 / SrTiO 3 superlattices, suggesting that the precise nature of domain walls in the ultrathin PbTiO 3 layers is more intricate than previously thought and deserves further attention. Published by the American Physical Society 2024

Most perovskite oxides belong to the Pbnm space group, composed of an anisotropic unit cell, A-site antipolar displacements, and oxygen octahedral tilts. Mapping the orientation of the orthorhombic unit cell in epitaxial heterostructures that consist of at least one Pbnm compound is often needed for understanding and controlling the different degrees of coupling established at their coherent interfaces and, therefore, their resulting physical properties. However, retrieving this information from the strain maps generated with high-resolution scanning transmission electron microscopy can be challenging, because the three pseudocubic lattice parameters are very similar in these systems. Here, we present a novel methodology for mapping the crystallographic orientation in Pbnm systems. It makes use of the geometrical phase analysis algorithm, as applied to aberration-corrected scanning transition electron microscopy images, but in an unconventional way. The method is fast and robust, giving real-space maps of the lattice orientations in Pbnm systems, from both cross section and plan-view geometries, and across large fields of view. As an example, we apply our methodology to rare-earth nickelate heterostructures, in order to investigate how the crystallographic orientation of these films depends on various structural constraints that are imposed by the underlying single crystal substrates. We observe that the resulting domain distributions and associated defect landscapes mainly depend on a competition between the epitaxial compressive/tensile and shear strains, together with the matching of atomic displacements at the substrate/film interface. The results point toward strategies for controlling these characteristics by appropriate substrate choice.

We investigate nanoscale domain engineering via epitaxial coupling in a set of SrRuO3/PbTiO3/SrRuO3 heterostructures epitaxially grown on (110)o-oriented DyScO3 substrates. The SrRuO3 layer thickness is kept at 55 unit cells, whereas the PbTiO3 layer is grown to thicknesses of 23, 45, and 90 unit cells. Through a combination of atomic force microscopy, x-ray diffraction, and high resolution scanning transmission electron microscopy studies, we find that above a certain critical thickness of the ferroelectric layer, the large structural distortions associated with the ferroelastic domains propagate through the top SrRuO3 layer, locally modifying the orientation of the orthorhombic SrRuO3 and creating a modulated structure that extends beyond the ferroelectric layer boundaries.

We study the complex ferroelastic/ferroelectric domain structure in the prototypical ferroelectric PbTiO3 epitaxially strained on (110)o-oriented DyScO3 substrates, using a combination of atomic force microscopy, laboratory and synchrotron x-ray diffraction, and high resolution scanning transmission electron microscopy. We observe that the anisotropic strain imposed by the orthorhombic substrate creates a large asymmetry in the domain configuration, with domain walls macroscopically aligned along one of the two in-plane directions. We show that the periodicity as a function of film thickness deviates from the Kittel law. As the ferroelectric film thickness increases, we find that the domain configuration evolves from flux-closure to a/c-phase, with a larger scale arrangement of domains into superdomains.

The discovery of superconductivity in doped infinite‐layer nickelate thin films has brought increased attention to the behavior of the doped perovskite phase. Despite this interest, the majority of existing studies pertain to hole‐doped perovskite rare‐earth nickelate thin films, while most electron‐doping studies have been performed on bulk materials so far. To tackle this imbalance, a detailed study that addresses doping of NdNiO₃ thin films using A‐site substitution is presented, using Pb as a dopant and taking advantage of its valence‐skipping nature. Through a combination of complementary techniques including X‐ray diffraction, transport measurements, X‐ray absorption spectroscopy, electron energy‐loss spectroscopy and scanning transmission electron microscopy, the valence of Pb in the Nd_1−xPb_xNiO₃ structure is confirmed to be 4+, and the behavior of the doped thin films is found to be controlled by a competition between carrier injection and structural distortions, which respectively reduce and increase the metal‐to‐insulator transition temperature. This work provides a systematic study of electron doping in NdNiO₃, demonstrating that A‐site substitution with Pb is an appropriate method for such doping in perovskite rare‐earth nickelate systems.

The layered structure of superconducting cuprates is considered to be a key ingredient to achieve high superconducting transition temperatures. In this work, we investigate the possibility of doping the SrCuO2 infinite-layer compound by inserting additional oxygen into its structure. We observe that the infinite-layer SrCuO2 structure is epitaxially stabilized in thin films grown by pulsed laser deposition in pure O2. Increasing the oxidizing power by introducing ozone during the growth leads to a different phase with an elongated c axis. Scanning transmission electron microscopy analysis suggests that the films with an elongated c axis are composed of SrCuO2.5 blocks separated by SrCuO2 layers arranged to match the substrate spacing. X-ray absorption spectroscopy measurements show that this SrCuO2+δ phase is associated with a more isotropic Cu orbital configuration and hole doping. This hole doping leads to a dramatic reduction in the resistivity of the films, with a magnitude that depends on the precise oxygen content in the structure.

We have grown single crystals of a new polymorph of Sr₂TiO₄. It contains titanium in an unusual tetrahedral coordination and transforms to the Ruddlesden–Popper structure with an interesting orientational relationship.

Simultaneous manipulation of multiple boundary conditions in nanoscale heterostructures offers a versatile route to stabilizing unusual structures and emergent phases. Here, we show that a stable supercrystal phase comprising a three-dimensional ordering of nanoscale domains with tailored periodicities can be engineered in PbTiO₃–SrRuO₃ ferroelectric–metal superlattices. A combination of laboratory and synchrotron X-ray diffraction, piezoresponse force microscopy, scanning transmission electron microscopy and phase-field simulations reveals a complex hierarchical domain structure that forms to minimize the elastic and electrostatic energy. Large local deformations of the ferroelectric lattice are accommodated by periodic lattice modulations of the metallic SrRuO₃ layers with curvatures up to 10⁷ m⁻¹. Our results show that multidomain ferroelectric systems can be exploited as versatile templates to induce large curvatures in correlated materials, and present a route for engineering correlated materials with modulated structural and electronic properties that can be controlled using electric fields.