Correlated Electron Oxides Research Articles

Picosecond Femtojoule Resistive Switching in Nanoscale VO2 Memristors.

Beyond-Moore computing technologies are expected to provide a sustainable alternative to the von Neumann approach not only due to their down-scaling potential but also via exploiting device-level functional complexity at the lowest possible energy consumption. The dynamics of the Mott transition in correlated electron oxides, such as vanadium dioxide, has been identified as a rich and reliable source of such functional complexity. However, its full potential in high-speed and low-power operation has been largely unexplored. We fabricated nanoscale VO2 devices embedded in a broadband test circuit to study the speed and energy limitations of their resistive switching operation. Our picosecond time-resolution, real-time resistive switching experiments and numerical simulations demonstrate that tunable low-resistance states can be set by the application of 20 ps long, <1.7 V amplitude voltage pulses at 15 ps incubation times and switching energies starting from a few femtojoule. Moreover, we demonstrate that at nanometer-scale device sizes not only the electric field induced insulator-to-metal transition but also the thermal conduction limited metal-to-insulator transition can take place at time scales of 100s of picoseconds. These orders of magnitude breakthroughs can be utilized to design high-speed and low-power dynamical circuits for a plethora of neuromorphic computing applications from pattern recognition to numerical optimization.

Modulation-doping a correlated electron insulator

Correlated electron materials (CEMs) host a rich variety of condensed matter phases. Vanadium dioxide (VO2) is a prototypical CEM with a temperature-dependent metal-to-insulator (MIT) transition with a concomitant crystal symmetry change. External control of MIT in VO2—especially without inducing structural changes—has been a long-standing challenge. In this work, we design and synthesize modulation-doped VO2-based thin film heterostructures that closely emulate a textbook example of filling control in a correlated electron insulator. Using a combination of charge transport, hard X-ray photoelectron spectroscopy, and structural characterization, we show that the insulating state can be doped to achieve carrier densities greater than 5 × 1021 cm−3 without inducing any measurable structural changes. We find that the MIT temperature (TMIT) continuously decreases with increasing carrier concentration. Remarkably, the insulating state is robust even at doping concentrations as high as ~0.2 e−/vanadium. Finally, our work reveals modulation-doping as a viable method for electronic control of phase transitions in correlated electron oxides with the potential for use in future devices based on electric-field controlled phase transitions.

Reversible phase transformation and comprehensive phase diagram in SrCoO2.5+x(0≤x≤0.5) with the electric field control of oxygen content

Oxygen deficiency plays an essential role in tailoring the intriguing physical properties of complex oxides that can be harnessed in the cutting-edge energy and information technologies. A fine and continuous control of the oxygen content to modulate the rich physical properties of the complex oxides is highly desirable for both basic research and modern electronic technologies. Here, we report a recently developed ionic field-effect transistor (iFET) device with a solid oxygen ionic conductor (OIC) as the gate dielectric to finely and continuously control the oxygen content of the oxides. We realize a reversible structural transformation between brownmillerite $\mathrm{SrCo}{\mathrm{O}}_{2.5}$ and perovskite $\mathrm{SrCo}{\mathrm{O}}_{3}$ by driving oxygen ions in and out of the samples with the OICFET at room temperature. With continuously changing the oxygen content, a comprehensive phase diagram of the $\mathrm{SrCo}{\mathrm{O}}_{2.5+x}$ $(0\ensuremath{\le}x\ensuremath{\le}0.5)$ thin film from an antiferromagnetic insulator to a ferromagnetic metal is obtained in a single device. Our work provides a promising route to continuously and reversibly regulate the oxygen content and to explore unique physical states in the correlated electron oxides, and represents an important step towards the realization of a long-standing goal to develop complex oxide based devices that can be integrated with existing technologies.

Tunable broadband terahertz properties in an architecture optimized ITO/VO2 hybrid metamaterial

This article proposes an architecture optimized indium-tin-oxide (ITO)/vanadium dioxide (VO2) hybrid metamaterial with optically transparent and tunable broadband terahertz properties. By changing the architecture of subunits, a broadband (∼1 THz) absorption with average absorptivity of 80.0 % has been achieved in an optimized ITO metamaterial at first. With adding strong correlated electron oxide VO2 film, the tunability is introduced in the ITO/VO2 hybrid structures. The most striking finding here is that the position of the VO2 layers in the hybrid structure can efficiently affect both the THz properties and the modulation functionality. In an optimized ITO/VO2 hybrid structure, 84.5 % reflection modulation and 78.9 % absorption modulation within a broadband (0.2 ∼1.0 THz) range are obtained. These findings highlight the architecture optimization for the THz properties in hybrid metamaterials, which is expected to have a great technological impact on the design of optically transparent THz tunable absorbers.

Active and Smart Terahertz Electro-Optic Modulator Based on VO2 Structure.

Modulating terahertz (THz) waves actively and smartly through an external field is highly desired in the development of THz spectroscopic devices. Here, we demonstrate an active and smart electro-optic THz modulator based on a strongly correlated electron oxide vanadium dioxide (VO2). With milliampere current excitation on the VO2 thin film, the transmission, reflection, absorption, and phase of THz waves can be modulated efficiently. In particular, the antireflection condition can be actively achieved and the modulation depth reaches 99.9%, accompanied by a 180° phase switching. Repeated and current scanning experiments confirm the high stability and multibit modulation of this electro-optic modulation. Most strikingly, by utilizing a feedback loop of "THz-electro-THz" geometry, a smart electro-optic THz control is realized. For instance, the antireflection condition can be stabilized precisely no matter what the initial condition is and how the external environment changes. The proposed electro-optic THz modulation method, taking advantage of strongly correlated electron material, opens up avenues for the realization of THz smart devices.

Effect of capping layers on the near-surface region of SrVO3 films

Surfaces of correlated electron oxides are of significant interest from both fundamental and applied perspectives. Many such oxides feature a near-surface region (NSR) that differs from the bulk’s properties. The NSR can significantly affect the interpretation of the material’s electronic structure, especially for those in thin film form, and have detrimental effects for applications such as field effect devices and catalysts. In this work, we study the changes in the composition and the electronic structure of the NSR of SrVO3 (SVO) thin films. We employ x-ray photoelectron spectroscopy (XPS) and compare TiOx-capped SVO films to identical uncapped films that were exposed to ambient conditions. The significant overoxidation of the SVO surface in the bare film, illustrated by a primary V5+ component, is prevented by the TiOx layer in the capped film. The capped film further exhibits a decrease in Sr surface phases. These results demonstrate the importance and potential of such capping layers in preserving the bulk properties of correlated oxides in their NSR, enabling more accurate probes for their underlying physics and offering a route for their integration into devices.

Large phonon drag thermopower boosted by massive electrons and phonon leaking in LaAlO3/LaNiO3/LaAlO3 heterostructure.

An unusually large thermopower (S) enhancement is induced by heterostructuring thin films of the strongly correlated electron oxide LaNiO3. The phonon-drag effect, which is not observed in bulk LaNiO3, enhances S for thin films compressively strained by LaAlO3 substrates. By a reduction in the layer thickness down to three unit cells and subsequent LaAlO3 surface termination, a 10 times S enhancement over the bulk value is observed due to large phonon drag S (Sg), and the Sg contribution to the total S occurs over a much wider temperature range up to 220 K. The Sg enhancement originates from the coupling of lattice vibration to the d electrons with large effective mass in the compressively strained ultrathin LaNiO3, and the electron–phonon interaction is largely enhanced by the phonon leakage from the LaAlO3 substrate and the capping layer. The transition-metal oxide heterostructures emerge as a new playground to manipulate electronic and phononic properties in the quest for high-performance thermoelectrics.

Reversible optical control of the metal-insulator transition across the epitaxial heterointerface of a VO2/Nb:TiO2 junction

Optical control of exotic properties in strongly correlated electron materials is very attractive owing to their potential applications in optical and electronic devices. Herein, we demonstrate a vertical heterojunction made of a correlated electron oxide thin film VO2 and a conductive 0.05 wt% Nb-doped TiO2 single crystal, whose metal-insulator transition (MIT) across the nanoscale heterointerface can be efficiently modulated by visible light irradiation. The magnitude of the MIT decreases from ~350 in the dark state to ~7 in the illuminated state, obeying a power law with respect to the light power density. The junction resistance is switched in a reversible and synchronous manner by turning light on and off. The optical tunability of it is also exponentially proportional to the light power density, and a 320-fold on/off ratio is achieved with an irradiance of 65.6 mW cm−2 below the MIT temperature. While the VO2 thin film is metallic above the MIT temperature, the optical tunability is remarkably weakened, with a one-fold change remaining under light illumination. These results are co-attributed to a net reduction (~15 meV) in the apparent barrier height and the photo-carrier-injection-induced metallization of the VO2 heterointerface through a photovoltaic effect, which is induced by deep defect level transition upon the visible light irradiance at low temperature. Additionally, the optical tunability is minimal, resulting from the quite weak modulation of the already metallic band structure in the Schottky-type junction above the MIT temperature. This work enables a remotely optical scheme to manipulate the MIT, implying potential uncooled photodetection and photoswitch applications.

Photoinduced Broad-band Tunable Terahertz Absorber Based on a VO2 Thin Film.

The demand for terahertz (THz) communication and detection fuels continuous research for high performance of THz absorption materials. In addition to varying the materials and their structure passively, an alternative approach is to modulate a THz wave actively by tuning an external stimulus. Correlated oxides are ideal materials for this because the effects of a small external control parameter can be amplified by inner electronic correlations. Here, by utilizing an unpatterned strongly correlated electron oxide VO2 thin film, a photoinduced broad-band tunable THz absorber is realized first. The absorption, transmission, reflection, and phase of THz waves can all be actively controlled by an external pump laser above room temperature. By varying the laser fluence, the average broad-band absorption can be tuned from 18.9 to 74.7% and the average transmission can be tuned from 9.2 to 69.2%. Meanwhile, a broad-band antireflection is obtained at 5.6 mJ/cm2, and a π-phase shift of a reflected THz wave is achieved when the fluence increases greater than 5.7 mJ/cm2. Apart from other modulators, the photoexcitation-assisted dual-phase competition is identified as the origin of this active THz multifunctional modulation. Our work suggests that advantages of controllable phase separation in strongly correlated electron systems could provide viable routes in the creation of active optical components for THz waves.

High pO2 Floating Zone Crystal Growth of the Perovskite Nickelate PrNiO3

Single crystals of PrNiO3 were grown under an oxygen pressure of 295 bar using a unique high-pressure optical-image floating zone furnace. The crystals, with volume in excess of 1 mm3, were characterized structurally using single crystal and powder X-ray diffraction. Resistivity, specific heat, and magnetic susceptibility were measured, all of which evidenced an abrupt, first order metal-insulator transition (MIT) at ~130 K, in agreement with previous literature reports on polycrystalline specimens. Temperature-dependent single crystal diffraction was performed to investigate changes through the MIT. Our study demonstrates the opportunity space for high fugacity, reactive environments for single crystal growth specifically of perovskite nickelates but more generally to correlated electron oxides.

Doublon-holon pairing mechanism via exchange interaction in two-dimensional cuprate Mott insulators.

Coupling of charge and spin degrees of freedom is a critical feature of correlated electron oxides, as represented by the spin-related mechanism of a Cooper pair under high-T c superconductivity. A doublon-holon pair generated on an antiferromagnetic spin background is also predicted to attract each other via the spin-spin interaction J, similar to a Cooper pair, while its evidence is difficult to obtain experimentally. Here, we investigate such an excitonic effect by electroreflectance spectroscopy using terahertz electric field pulses in undoped cuprates: Nd2CuO4, Sr2CuO2Cl2, and La2CuO4. Analyses of the spectral changes of reflectivity under electric fields reveal that the splitting of odd-parity and even-parity excitons, a measure of doublon-holon binding energy, increases with J. This trend is reproduced by t-J-type model calculations, providing strong evidence of the spin-related doublon-holon pairing. Agreement with the calculations supports the s-wave symmetry of the doublon-holon pair in contrast to the d-wave Cooper pair in doped cuprates.

Ferroelectric polarization-controlled resistive switching in BaTiO3/SmNiO3 epitaxial heterostructures

As an emerging phenomenon in oxide heterostructures, the ferroelectric control of electronic transport is attracting considerable research attention. However, the effect of ferroelectric polarization on resistive switching (RS) remains controversial. In this study, to determine the effects of ferroelectric polarization on memory characteristics, ferroelectric and non-ferroelectric BaTiO3 (BTO) films were fabricated using different oxygen partial pressures (Po2) during film growth. A correlated electron oxide, SmNiO3 (SNO), was selected as the bottom electrode. Based on piezoelectric force microscopy, ferroelectricity was verified in the BTO films prepared at Po2 ≥ 3 Pa, whereas the films fabricated at lower Po2 did not exhibit ferroelectricity. Remarkable RS with an ON/OFF ratio of 104% was clearly observed in heterostructures containing ferroelectric BTO, while RS was negligible in structures with non-ferroelectric BTO. The strong ferroelectricity dependence of RS behavior on the BTO/SNO heterostructures was attributed to the ferroelectric control of device transport between bulk-limited current in the low-resistance state and interface-limited conductance in the high-resistance state, which results from the modulation of the potential barrier at the BTO/SNO interface. The findings provide strong evidence for the dominant effect of ferroelectric polarization of BTO on the transport properties of BTO/SNO heterostructures.

Enhancement of electronic-transport switching in single-crystal narrower VO2 nanowire channels through side-gate electric fields

Investigations of electric field-induced resistance modulation in correlated electron oxides with a metal-insulator transition play a significant role in understanding the behavior of nano-domains via electric perturbation and in paving the way for steep slope switching applications. Here, we report the dependence of the resistance switching effect on both the width of oxide nanowires and their crystallinity in VO2-based planar-type field effect transistors with an air nano-gap gate. A positive electric field yielded an expansion of the metallic nano-domains, while a negative one caused a depletion layer to form. Moreover, narrower VO2 nanowires and single crystal VO2 nanowires showed effective resistance modulation when the gate bias was varied. Our results provide an understanding of the electronic characteristics in metal-insulator nano-domains through carrier modulation and further the development of devices employing metal–insulator nano-domains.

Tunable single-phase magnetic behavior in chemically synthesized AFeO3-MFe2O4 (A = Bi or La, M = Co or Ni) nanocomposites.

The properties of magnetic nanocomposites rely strongly on the interplay between those of the constituent components. When the individual components themselves are complex systems belonging to the family of correlated electron oxide systems which typically exhibit exotic physical properties, it becomes nontrivial to customize the properties of the nanocomposite. In this paper, we demonstrate an easy, but effective method to synthesize and tune the magnetic properties of nanocomposites consisting of correlated electron oxide systems as the individual components. Our method is based on a novel synthesis technique by which the two components of the nanocomposite can be directly integrated with each other, yielding homogeneous samples on the nanoscale with magnetic behavior reminiscent of a single phase. We illustrate our method using multiferroic BiFeO3 (BFO) and LaFeO3 (LFO) as the major phase (i.e., matrix), and MFe2O4 (M = Co2+ or Ni2+) as the embedded magnetic phase. Furthermore, we show that by a proper selection of the second phase in the nanocomposite, it is possible to customize the magnetic properties of the matrix. We illustrate this by choosing CoFe2O4 and NiFe2O4, two oxides with widely differing magnetic anisotropies, as the embedded phase, and demonstrate that the coercivity of BFO and LFO can be increased or decreased depending on the choice of the embedded phase in the nanocomposite.

High-Pressure Floating-Zone Growth of Perovskite Nickelate LaNiO3 Single Crystals

We report the first single crystal growth of the correlated metal LaNiO3 using a high-pressure optical-image floating zone furnace. The crystals were studied using single crystal/powder x-ray diffraction, resistivity, specific heat, and magnetic susceptibility. The availability of bulk LaNiO3 crystals will (i) promote deep understanding in this correlated material, including the mechanism of enhanced paramagnetic susceptibility, and (ii) provide rich opportunities as a substrate for thin film growth such as important ferroelectric and/or multiferroic materials. This study demonstrates the power of high pO2 single crystal growth of nickelate perovskites and correlated electron oxides more generally.

Magneto-tunable photocurrent in manganite-based heterojunctions.

Correlated electron oxide heterojunctions and their photovoltaic effect have attracted increasing attention from the viewpoints of both possible application to novel devices and basic science. In such junctions, correlated electron physics has to be taken into account in addition to conventional semiconductor modelling to explain distinctively emerging features. However, extracting novel functionalities has not been easy because it is not possible to predict their interfacial properties solely from their bulk characteristics. Here we describe a magneto-tunable photocurrent in a pn junction based on a correlated electron oxide La0.7Sr0.3MnO3 combined with a semiconducting SrTiO3 substrate. On applying an epitaxial strain, the photocurrent is enhanced threefold, which is increased 30% further by a magnetic field. Such a magneto-tunable effect is possible for only a narrow window of the correlated gap, which is itself adjusted by bandwidth and temperature. These results provide a guideline for utilization of correlated phenomena into the novel electronic devices.

Orientational Tuning of the Fermi Sea of Confined Electrons at theSrTiO3(110) and (111) Surfaces

We report the existence of confined electronic states at the (110) and (111) surfaces of SrTiO3. Using angle-resolved photoemission spectroscopy, we find that the corresponding Fermi surfaces, subband masses, and orbital ordering are different from the ones at the (001) surface of SrTiO3. This occurs because the crystallographic symmetries of the surface and sub-surface planes, and the electron effective masses along the confinement direction, influence the symmetry of the electronic structure and the orbital ordering of the t2g manifold. Remarkably, our analysis of the data also reveals that the carrier concentration and thickness are similar for all three surface orientations, despite their different polarities. The orientational tuning of the microscopic properties of two-dimensional electron states at the surface of SrTiO3 echoes the tailoring of macroscopic (e.g. transport) properties reported recently in LaAlO3/SrTiO3 (110) and (111) interfaces, and is promising for searching new types of 2D electronic states in correlated-electron oxides.

Subnanosecond incubation times for electric-field-induced metallization of a correlated electron oxide.

Strong interactions, or correlations, between the d or f electrons in transition-metal oxides lead to various types of metal-insulator transitions that can be triggered by external parameters such as temperature, pressure, doping, magnetic fields and electric fields. Electric-field-induced metallization of such materials from their insulating states could enable a new class of ultrafast electronic switches and latches. However, significant questions remain about the detailed nature of the switching process. Here, we show, in the canonical metal-to-insulator transition system V₂O₃, that ultrafast voltage pulses result in its metallization only after an incubation time that ranges from ∼150 ps to many nanoseconds, depending on the electric field strength. We show that these incubation times can be accounted for by purely thermal effects and that intrinsic electronic-switching mechanisms may only be revealed using larger electric fields at even shorter timescales.

Tunneling Electroresistance Induced by Interfacial Phase Transitions in Ultrathin Oxide Heterostructures

The ferroelectric (FE) control of electronic transport is one of the emerging technologies in oxide heterostructures. Many previous studies in FE tunnel junctions (FTJs) exploited solely the differences in the electrostatic potential across the FTJs that are induced by changes in the FE polarization direction. Here, we show that in practice the junction current ratios between the two polarization states can be further enhanced by the electrostatic modification in the correlated electron oxide electrodes, and that FTJs with nanometer thin layers can effectively produce a considerably large electroresistance ratio at room temperature. To understand these surprising results, we employed an additional control parameter, which is related to the crossing of electronic and magnetic phase boundaries of the correlated electron oxide. The FE-induced phase modulation at the heterointerface ultimately results in an enhanced electroresistance effect. Our study highlights that the strong coupling between degrees of freedom across heterointerfaces could yield versatile and novel applications in oxide electronics.

Strongly coupled phase transition in ferroelectric/correlated electron oxide heterostructures

We fabricated ultrathin ferroelectric/correlated electron oxide heterostructures composed of the ferroelectric Pb(Zr0.2Ti0.8)O3 and the correlated electron oxide (CEO) La0.8Sr0.2MnO3 on SrTiO3 substrates by pulsed laser epitaxy. The hole accumulation in the ultrathin CEO layer was substantially modified by heterostructuring with the ferroelectric layer, resulting in an insulator-metal transition. In particular, our thickness dependent study showed that drastic changes in transport and magnetic properties were strongly coupled to the modulation of charge carriers by ferroelectric field effect, which was confined to the vicinity of the interface. Thus, our results provide crucial evidence that strong ferroelectric field effect control can be achieved in ultrathin (10 nm) heterostructures, yielding at least a 100 000-fold change in resistivity.