Quantum Confinement and Electronic Structure at the Surface of van der Waals Ferroelectric α-In2Se3.

Two-dimensional (2D) ferroelectric (FE) materials are promising compounds for next-generation nonvolatile memories due to their low energy consumption and high endurance. Among them, α-In2Se3 has drawn particular attention due to its in- and out-of-plane ferroelectricity, whose robustness has been demonstrated down to the monolayer limit. This is a relatively uncommon behavior since most bulk FE materials lose their ferroelectric character at the 2D limit due to the depolarization field. Using angle resolved photoemission spectroscopy (ARPES), we unveil another unusual 2D phenomenon appearing in 2H α-In2Se3 single crystals, the occurrence of a highly metallic two-dimensional electron gas (2DEG) at the surface of vacuum-cleaved crystals. This 2DEG exhibits two confined states, which correspond to an electron density of approximately 1013 electrons/cm2, also confirmed by thermoelectric measurements. Combination of ARPES and density functional theory (DFT) calculations reveals a direct band gap of energy equal to 1.3 ± 0.1 eV, with the bottom of the conduction band localized at the center of the Brillouin zone, just below the Fermi level. Such strong n-type doping further supports the quantum confinement of electrons and the formation of the 2DEG.

Quantitative investigation of polarization-dependent photocurrent in ferroelectric thin films.

Ferroelectric thin films are investigated for their potential in photovoltaic (PV) applications, owing to their high open-circuit voltage and switchable photovoltaic effect. The direction of the ferroelectric polarization can control the sign of the photocurrent through the ferroelectric layer, theoretically allowing for 100% switchability of the photocurrent with the polarization, which is particularly interesting for photo-ferroelectric memories. However, the quantitative relationship between photocurrent and polarization remains little studied. In this work, a careful investigation of the polarization-dependent photocurrent of epitaxial Pb(Zr, Ti)O3thin films has been carried out, and has provided a quantitative determination of the unswitchable part of ferroelectric polarization. These results represent a systematic approach to study and optimize the switchability of photocurrent, and more broadly to get important insights on the ferroelectric behavior in all types of ferroelectric layers in which pinned polarization is difficult to investigate.

Reversible oxygen migration and phase transitions in hafnia-based ferroelectric devices.

Unconventional ferroelectricity exhibited by hafnia-based thin films-robust at nanoscale sizes-presents tremendous opportunities in nanoelectronics. However, the exact nature of polarization switching remains controversial. We investigated a La0.67Sr0.33MnO3/Hf0.5Zr0.5O2 capacitor interfaced with various top electrodes while performing in situ electrical biasing using atomic-resolution microscopy with direct oxygen imaging as well as with synchrotron nanobeam diffraction. When the top electrode is oxygen reactive, we observe reversible oxygen vacancy migration with electrodes as the source and sink of oxygen and the dielectric layer acting as a fast conduit at millisecond time scales. With nonreactive top electrodes and at longer time scales (seconds), the dielectric layer also acts as an oxygen source and sink. Our results show that ferroelectricity in hafnia-based thin films is unmistakably intertwined with oxygen voltammetry.

Understanding nanoscale structural distortions in Pb(Zr0.2Ti0.8)O3 by utilizing X-ray nanodiffraction and clustering algorithm analysis.

Hard X-ray nanodiffraction provides a unique nondestructive technique to quantify local strain and structural inhomogeneities at nanometer length scales. However, sample mosaicity and phase separation can result in a complex diffraction pattern that can make it challenging to quantify nanoscale structural distortions. In this work, a k-means clustering algorithm was utilized to identify local maxima of intensity by partitioning diffraction data in a three-dimensional feature space of detector coordinates and intensity. This technique has been applied to X-ray nanodiffraction measurements of a patterned ferroelectric PbZr0.2Ti0.8O3 sample. The analysis reveals the presence of two phases in the sample with different lattice parameters. A highly heterogeneous distribution of lattice parameters with a variation of 0.02 Šwas also observed within one ferroelectric domain. This approach provides a nanoscale survey of subtle structural distortions as well as phase separation in ferroelectric domains in a patterned sample.

A rhombohedral ferroelectric phase in epitaxially strained Hf0.5Zr0.5O2 thin films.

Hafnia-based thin films are a favoured candidate for the integration of robust ferroelectricity at the nanoscale into next-generation memory and logic devices. This is because their ferroelectric polarization becomes more robust as the size is reduced, exposing a type of ferroelectricity whose mechanism still remains to be understood. Thin films with increased crystal quality are therefore needed. We report the epitaxial growth of Hf0.5Zr0.5O2 thin films on (001)-oriented La0.7Sr0.3MnO3/SrTiO3 substrates. The films, which are under epitaxial compressive strain and predominantly (111)-oriented, display large ferroelectric polarization values up to 34 µC cm-2 and do not need wake-up cycling. Structural characterization reveals a rhombohedral phase, different from the commonly reported polar orthorhombic phase. This finding, in conjunction with density functional theory calculations, allows us to propose a compelling model for the formation of the ferroelectric phase. In addition, these results point towards thin films of simple oxides as a vastly unexplored class of nanoscale ferroelectrics.

Universal Fabrication of 2D Electron Systems in Functional Oxides.

2D electron systems (2DESs) in functional oxides are promising for applications, but their fabrication and use, essentially limited to SrTiO3 -based heterostructures, are hampered by the need for growing complex oxide overlayers thicker than 2 nm using evolved techniques. It is demonstrated that thermal deposition of a monolayer of an elementary reducing agent suffices to create 2DESs in numerous oxides.

X-ray diffraction imaging of metal-oxide epitaxial tunnel junctions made by optical lithography: use of focused and unfocused X-ray beams.

X-ray diffraction techniques are used in imaging mode in order to characterize micrometre-sized objects. The samples used as models are metal-oxide tunnel junctions made by optical lithography, with lateral sizes ranging from 150 µm down to 10 µm and various shapes: discs, squares and rectangles. Two approaches are described and compared, both using diffraction contrast: full-field imaging (topography) and raster imaging (scanning probe) using a micrometre-sized focused X-ray beam. It is shown that the full-field image gives access to macroscopic distortions (e.g. sample bending), while the local distortions, at the micrometre scale (e.g. tilts of the crystalline planes in the vicinity of the junction edges), can be accurately characterized only using focused X-ray beams. These local defects are dependent on the junction shape and larger by one order of magnitude than the macroscopic curvature of the sample.