Generation of Tunable Stochastic Sequences Using the Insulator-Metal Transition.

Probabilistic computing is a paradigm in which data are not represented by stable bits, but rather by the probability of a metastable bit to be in a particular state. The development of this technology has been hindered by the availability of hardware capable of generating stochastic and tunable sequences of "1s" and "0s". The options are currently limited to complex CMOS circuitry and, recently, magnetic tunnel junctions. Here, we demonstrate that metal-insulator transitions can also be used for this purpose. We use an electrical pump/probe protocol and take advantage of the stochastic relaxation dynamics in VO2 to induce random metallization events. A simple latch circuit converts the metallization sequence into a random stream of 1s and 0s. The resetting pulse in between probes decorrelates successive events, providing a true stochastic digital sequence.

Designing and controlling the properties of transition metal oxide quantum materials.

This Perspective addresses the design, creation, characterization and control of synthetic quantum materials with strong electronic correlations. We show how emerging synergies between theoretical/computational approaches and materials design/experimental probes are driving recent advances in the discovery, understanding and control of new electronic behaviour in materials systems with interesting and potentially technologically important properties. The focus here is on transition metal oxides, where electronic correlations lead to a myriad of functional properties including superconductivity, magnetism, Mott transitions, multiferroicity and emergent behaviour at picoscale-designed interfaces. Current opportunities and challenges are also addressed, including possible new discoveries of non-equilibrium phenomena and optical control of correlated quantum phases of transition metal oxides.

Negative capacitance in multidomain ferroelectric superlattices.

The stability of spontaneous electrical polarization in ferroelectrics is fundamental to many of their current applications, which range from the simple electric cigarette lighter to non-volatile random access memories. Research on nanoscale ferroelectrics reveals that their behaviour is profoundly different from that in bulk ferroelectrics, which could lead to new phenomena with potential for future devices. As ferroelectrics become thinner, maintaining a stable polarization becomes increasingly challenging. On the other hand, intentionally destabilizing this polarization can cause the effective electric permittivity of a ferroelectric to become negative, enabling it to behave as a negative capacitance when integrated in a heterostructure. Negative capacitance has been proposed as a way of overcoming fundamental limitations on the power consumption of field-effect transistors. However, experimental demonstrations of this phenomenon remain contentious. The prevalent interpretations based on homogeneous polarization models are difficult to reconcile with the expected strong tendency for domain formation, but the effect of domains on negative capacitance has received little attention. Here we report negative capacitance in a model system of multidomain ferroelectric-dielectric superlattices across a wide range of temperatures, in both the ferroelectric and paraelectric phases. Using a phenomenological model, we show that domain-wall motion not only gives rise to negative permittivity, but can also enhance, rather than limit, its temperature range. Our first-principles-based atomistic simulations provide detailed microscopic insight into the origin of this phenomenon, identifying the dominant contribution of near-interface layers and paving the way for its future exploitation.

Near-Atomic-Scale Mapping of Electronic Phases in Rare Earth Nickelate Superlattices.

Nanoscale mapping of the distinct electronic phases characterizing the metal-insulator transition displayed by most of the rare-earth nickelate compounds is fundamental for discovering the true nature of this transition and the possible couplings that are established at the interfaces of nickelate-based heterostructures. Here, we demonstrate that this can be accomplished by using scanning transmission electron microscopy in combination with electron energy-loss spectroscopy. By tracking how the O K and Ni L edge fine structures evolve across two different NdNiO3/SmNiO3 superlattices, displaying either one or two metal-insulator transitions depending on the individual layer thickness, we are able to determine the electronic state of each of the individual constituent materials. We further map the spatial configuration associated with their metallic/insulating regions, reaching unit cell spatial resolution. With this, we estimate the width of the metallic/insulating boundaries at the NdNiO3/SmNiO3 interfaces, which is measured to be on the order of four unit cells.

Length scales of interfacial coupling between metal and insulator phases in oxides.

Controlling phase transitions in transition metal oxides remains a central feature of both technological and fundamental scientific relevance. A well-known example is the metal-insulator transition, which has been shown to be highly controllable. However, the length scale over which these phases can be established is not yet well understood. To gain insight into this issue, we atomically engineered an artificially phase-separated system through fabricating epitaxial superlattices that consist of SmNiO3 and NdNiO3, two materials that undergo a metal-to-insulator transition at different temperatures. We demonstrate that the length scale of the interfacial coupling between metal and insulator phases is determined by balancing the energy cost of the boundary between a metal and an insulator and the bulk phase energies. Notably, we show that the length scale of this effect exceeds that of the physical coupling of structural motifs, which introduces a new framework for interface-engineering properties at temperatures against the bulk energetics.

Thickness-Dependent Perovskite Octahedral Distortions at Heterointerfaces.

In this study, we analyze how the octahedral tilts and rotations of thin films of LaNiO3 and LaAlO3 grown on different substrates, determined using synchrotron X-ray diffraction-measured half-integer Bragg peaks, depend upon the total film thickness. We find a striking difference between films grown on SrTiO3 and LaAlO3 substrates which appears to stem not only from the difference in epitaxial strain state but also from the level of continuity at the heterointerface. In particular, the chemically and structurally discontinuous LaNiO3/SrTiO3 and LaAlO3/SrTiO3 interfaces cause a large variation in the octahedral network as a function of film thickness whereas the rather continuous LaNiO3/LaAlO3 interface seems to allow from just a few unit cells the formation of a stable octahedral pattern corresponding to that expected only given the applied biaxial strain.

Tuning of the depolarization field and nanodomain structure in ferroelectric thin films.

The screening efficiency of a metal-ferroelectric interface plays a critical role in determining the polarization stability and hence the functional properties of ferroelectric thin films. Imperfect screening leads to strong depolarization fields that reduce the spontaneous polarization or drive the formation of ferroelectric domains. We demonstrate that by modifying the screening at the metal-ferroelectric interface through insertion of ultrathin dielectric spacers, the strength of the depolarization field can be tuned and thus used to control the formation of nanoscale domains. Using piezoresponse force microscopy, we follow the evolution of the domain configurations as well as polarization stability as a function of depolarization field strength.

Improper ferroelectricity in perovskite oxide artificial superlattices.

Ferroelectric thin films and superlattices are currently the subject of intensive research because of the interest they raise for technological applications and also because their properties are of fundamental scientific importance. Ferroelectric superlattices allow the tuning of the ferroelectric properties while maintaining perfect crystal structure and a coherent strain, even throughout relatively thick samples. This tuning is achieved in practice by adjusting both the strain, to enhance the polarization, and the composition, to interpolate between the properties of the combined compounds. Here we show that superlattices with very short periods possess a new form of interface coupling, based on rotational distortions, which gives rise to 'improper' ferroelectricity. These observations suggest an approach, based on interface engineering, to produce artificial materials with unique properties. By considering ferroelectric/paraelectric PbTiO3/SrTiO3 multilayers, we first show from first principles that the ground-state of the system is not purely ferroelectric but also primarily involves antiferrodistortive rotations of the oxygen atoms in a way compatible with improper ferroelectricity. We then demonstrate experimentally that, in contrast to pure PbTiO3 and SrTiO3 compounds, the multilayer system indeed behaves like a prototypical improper ferroelectric and exhibits a very large dielectric constant of epsilon(r) approximately 600, which is also fairly temperature-independent. This behaviour, of practical interest for technological applications, is distinct from that of normal ferroelectrics, for which the dielectric constant is typically large but strongly evolves around the phase transition temperature and also differs from that of previously known improper ferroelectrics that exhibit a temperature-independent but small dielectric constant only.

Exchange bias in LaNiO3-LaMnO3 superlattices.

The wide spectrum of exotic properties exhibited by transition-metal oxides stems from the complex competition between several quantum interactions. The capacity to select the emergence of specific phases at will is nowadays extensively recognized as key for the design of diverse new devices with tailored functionalities. In this context, interface engineering in complex oxide heterostructures has developed into a flourishing field, enabling not only further tuning of the exceptional properties of these materials, but also giving access to hidden phases and emergent physical phenomena. Here we demonstrate how interfacial interactions can induce a complex magnetic structure in a non-magnetic material. We specifically show that exchange bias can unexpectedly emerge in heterostructures consisting of paramagnetic LaNiO3 (LNO) and ferromagnetic LaMnO3 (LMO). The observation of exchange bias in (111)-oriented LNO-LMO superlattices, manifested as a shift of the magnetization-field loop, not only implies the development of interface-induced magnetism in the paramagnetic LNO layers, but also provides us with a very subtle tool for probing the interfacial coupling between the LNO and LMO layers. First-principles calculations indicate that this interfacial interaction may give rise to an unusual spin order, resembling a spin-density wave, within the LNO layers.

Metal-insulator transition in composition-tuned nickel oxide films.

Thin films of the solid solution Nd1-xLaxNiO3are grown in order to study the expected 0 K phase transitions at a specific composition. We experimentally map out the structural, electronic and magnetic properties as a function ofxand a discontinuous, possibly first order, insulator-metal transition is observed at low temperature whenx= 0.2. Raman spectroscopy and scanning transmission electron microscopy show that this is not associated with a correspondingly discontinuous global structural change. On the other hand, results from density functional theory (DFT) and combined DFT and dynamical mean field theory calculations produce a 0 K first order transition at around this composition. We further estimate the temperature-dependence of the transition from thermodynamic considerations and find that a discontinuous insulator-metal transition can be reproduced theoretically and implies a narrow insulator-metal phase coexistence withx. Finally, muon spin rotation (µSR) measurements suggest that there are non-static magnetic moments in the system that may be understood in the context of the first order nature of the 0 K transition and its associated phase coexistence regime.

Thermal and electrostatic tuning of surface phonon-polaritons in LaAlO3/SrTiO3 heterostructures.

Phonon polaritons are promising for infrared applications due to a strong light-matter coupling and subwavelength energy confinement they offer. Yet, the spectral narrowness of the phonon bands and difficulty to tune the phonon polariton properties hinder further progress in this field. SrTiO3 - a prototype perovskite oxide - has recently attracted attention due to two prominent far-infrared phonon polaritons bands, albeit without any tuning reported so far. Here we show, using cryogenic infrared near-field microscopy, that long-propagating surface phonon polaritons are present both in bare SrTiO3 and in LaAlO3/SrTiO3 heterostructures hosting a two-dimensional electron gas. The presence of the two-dimensional electron gas increases dramatically the thermal variation of the upper limit of the surface phonon polariton band due to temperature dependent polaronic screening of the surface charge carriers. Furthermore, we demonstrate a tunability of the upper surface phonon polariton frequency in LaAlO3/SrTiO3 via electrostatic gating. Our results suggest that oxide interfaces are a new platform bridging unconventional electronics and long-wavelength nanophotonics.

Scale-invariant magnetic textures in the strongly correlated oxide NdNiO3.

Strongly correlated quantum solids are characterized by an inherently granular electronic fabric, with spatial patterns that can span multiple length scales in proximity to a critical point. Here, we use a resonant magnetic X-ray scattering nanoprobe with sub-100 nm spatial resolution to directly visualize the texture of antiferromagnetic domains in NdNiO3. Surprisingly, our measurements reveal a highly textured magnetic fabric, which we show to be robust and nonvolatile even after thermal erasure across its ordering temperature. The scale-free distribution of antiferromagnetic domains and its non-integral dimensionality point to a hitherto-unobserved magnetic fractal geometry in this system. These scale-invariant textures directly reflect the continuous nature of the magnetic transition and the proximity of this system to a critical point. The present study not only exposes the near-critical behavior in rare earth nickelates but also underscores the potential for X-ray scattering nanoprobes to image the multiscale signatures of criticality near a critical point.

High sensitivity variable-temperature infrared nanoscopy of conducting oxide interfaces.

Probing the local transport properties of two-dimensional electron systems (2DES) confined at buried interfaces requires a non-invasive technique with a high spatial resolution operating in a broad temperature range. In this paper, we investigate the scattering-type scanning near field optical microscopy as a tool for studying the conducting LaAlO3/SrTiO3 interface from room temperature down to 6 K. We show that the near-field optical signal, in particular its phase component, is highly sensitive to the transport properties of the electron system present at the interface. Our modeling reveals that such sensitivity originates from the interaction of the AFM tip with coupled plasmon-phonon modes with a small penetration depth. The model allows us to quantitatively correlate changes in the optical signal with the variation of the 2DES transport properties induced by cooling and by electrostatic gating. To probe the spatial resolution of the technique, we image conducting nano-channels written in insulating heterostructures with a voltage-biased tip of an atomic force microscope.

Probing Quantum Confinement and Electronic Structure at Polar Oxide Interfaces.

Polar discontinuities occurring at interfaces between two materials constitute both a challenge and an opportunity in the study and application of a variety of devices. In order to cure the large electric field occurring in such structures, a reconfiguration of the charge landscape sets in at the interface via chemical modifications, adsorbates, or charge transfer. In the latter case, one may expect a local electronic doping of one material: one example is the two-dimensional electron liquid (2DEL) appearing in SrTiO3 once covered by a polar LaAlO3 layer. Here, it is shown that tuning the formal polarization of a (La,Al)1-x (Sr,Ti) x O3 (LASTO:x) overlayer modifies the quantum confinement of the 2DEL in SrTiO3 and its electronic band structure. The analysis of the behavior in magnetic field of superconducting field-effect devices reveals, in agreement with ab initio calculations and self-consistent Poisson-Schrödinger modeling, that quantum confinement and energy splitting between electronic bands of different symmetries strongly depend on the interface total charge densities. These results strongly support the polar discontinuity mechanisms with a full charge transfer to explain the origin of the 2DEL at the celebrated LaAlO3/SrTiO3 interface and demonstrate an effective tool for tailoring the electronic structure at oxide interfaces.

Conductivity and Local Structure of LaNiO3 Thin Films.

A marked conductivity enhancement is reported in 6-11 unit cell LaNiO3 thin films. A maximal conductivity is also observed in ab initio calculations for films of the same thickness. In agreement with results from state of the art scanning transmission electron microscopy, the calculations also reveal a differentiated film structure comprising characteristic surface, interior, and heterointerface structures. Based on this observation, a three-element parallel conductor model is considered and leads to the conclusion that the conductivity enhancement for films of 6-11 unit cells, stems from the onset of intercompetition between the three local structures in the film depth.

Advanced fabrication and characterization of epitaxial ferroelectric thin films and multilayers.

Understanding the behavior of ferroelectrics on the nanoscale level requires the production of materials of the highest quality and advanced characterization techniques for probing the fascinating properties of these systems with reduced dimensions. Here we give an overview of our recent achievements in this area, which includes the detailed study of the suppression of ferroelectricity in PbTiO3 thin films, the fabrication of PbTiO3/SrTiO3 superlattices in which ferroelectricity shows some surprising behavior, and finally the manipulation of nanoscale ferroelectric domains using the atomic force microscope which leads to the precise analysis of domain wall creep and roughness in Pb(Zr,Ti)O3 thin films.