Atomically engineered interfaces yield extraordinary electrostriction.

Electrostriction is a property of dielectric materials whereby an applied electric field induces a mechanical deformation proportional to the square of that field. The magnitude of the effect is usually minuscule (<10-19 m2 V-2 for simple oxides). However, symmetry-breaking phenomena at the interfaces can offer an efficient strategy for the design of new properties1,2. Here we report an engineered electrostrictive effect via the epitaxial deposition of alternating layers of Gd2O3-doped CeO2 and Er2O3-stabilized δ-Bi2O3 with atomically controlled interfaces on NdGaO3 substrates. The value of the electrostriction coefficient achieved is 2.38 × 10-14 m2 V-2, exceeding the best known relaxor ferroelectrics by three orders of magnitude. Our theoretical calculations indicate that this greatly enhanced electrostriction arises from coherent strain imparted by interfacial lattice discontinuity. These artificial heterostructures open a new avenue for the design and manipulation of electrostrictive materials and devices for nano/micro actuation and cutting-edge sensors.

Strain Engineering: Perfecting Freestanding Perovskite Oxide Fabrication.

Freestanding oxide membranes provide a promising path for integrating devices on silicon and flexible platforms. To ensure optimal device performance, these membranes must be of high crystal quality, stoichiometric, and their morphology free from cracks and wrinkles. Often, layers transferred on substrates show wrinkles and cracks due to a lattice relaxation from an epitaxial mismatch. Doping the sacrificial layer of Sr3Al2O6 (SAO) with Ca or Ba offers a promising solution to overcome these challenges, yet its effects remain critically underexplored. A systematic study of doping Ca into SAO is presented, optimizing the pulsed laser deposition (PLD) conditions, and adjusting the supporting polymer type and thickness, demonstrating that strain engineering can effectively eliminate these imperfections. Using SrTiO3 as a case study, it is found that Ca1.5Sr1.5Al2O6 offers a near-perfect match and a defect-free freestanding membrane. This approach, using the water-soluble Bax/CaxSr3-xAl2O6 family, paves the way for producing high-quality, large freestanding membranes for functional oxide devices.

A Two-Dimensional Superconducting Electron Gas in Freestanding LaAlO3/SrTiO3 Micromembranes.

Freestanding oxide membranes constitute an intriguing material platform for new functionalities and allow integration of oxide electronics with technologically important platforms such as silicon. Sambri et al. recently reported a method to fabricate freestanding LaAlO3/SrTiO3 (LAO/STO) membranes by spalling of strained heterostructures. Here, we first develop a scheme for the high-yield fabrication of membrane devices on silicon. Second, we show that the membranes exhibit metallic conductivity and a superconducting phase below ∼200 mK. Using anisotropic magnetotransport we extract the superconducting phase coherence length ξ ≈ 36-80 nm and establish an upper bound on the thickness of the superconducting electron gas d ≈ 17-33 nm, thus confirming its two-dimensional character. Finally, we show that the critical current can be modulated using a silicon-based backgate. The ability to form superconducting nanostructures of LAO/STO membranes, with electronic properties similar to those of the bulk counterpart, opens opportunities for integrating oxide nanoelectronics with silicon-based architectures.

On the thermoelectric properties of Nb-doped SrTiO3 epitaxial thin films.

The exploration for thermoelectric thin films of complex oxides such as SrTiO3-based oxides is driven by the need for miniaturized harvesting devices for powering the Internet of Things (IoT). However, there is still not a clear consensus in the literature for the underlying influence of film thickness on thermoelectric properties. Here, we report the fabrication of epitaxial thin films of 6% Nb-doped SrTiO3 on (001) (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) single crystal using pulsed laser deposition (PLD) where the film thickness was varied from 2 nm to 68 nm. The thickness dependence shows a subtle increase of tetragonality of the thin film lattice and a gradual drop of the electrical conductivity, the density of charge carriers, and the thermoelectric Seebeck coefficient as the film thickness decreases. DFT-based calculations show that ∼2.8% increase in tetragonality results in an increased splitting between t2g and eg orbitals to ∼42.3 meV. However, experimentally observed tetragonality for films between 68 to 13 nm is only 0.06%. Hence, the effect of thickness on tetragonality is neglected. We have discussed the decrease of conductivity and the Seebeck coefficient based on the decrease of carriers and change in the scattering mechanism, respectively.

Ba2-xBixCoRuO6 (0.0 ≤ x ≤ 0.6) Hexagonal Double-Perovskite-Type Oxides as Promising p-Type Thermoelectric Materials.

A new series of Ba2-xBixCoRuO6 (0.0 ≤ x ≤ 0.6) hexagonal double perovskite oxides have been synthesized by a solid-state reaction method by substituting Ba with Bi. The polycrystalline materials are structurally characterized by the laboratory X-ray diffraction, synchrotron X-ray, and neutron powder diffraction. The lattice parameters are found to increase with increasing Bi doping despite the smaller ionic radius of Bi3+ compared to Ba2+. The expansion is attributed to the reduction of Co/Ru-site cations. Scanning electron microscopy further shows that the grain size increases with the Bi content. All Ba2-xBixCoRuO6 (0.0 ≤ x ≤ 0.6) samples exhibit p-type behavior, and the electrical resistivity (ρ) is consistent with a small polaron hopping model. The Seebeck coefficient (S) and thermal conductivity (κ) are improved significantly with Bi doping. High values of the power factor (PF ∼ 6.64 × 10-4 W/m·K2) and figure of merit (zT ∼ 0.23) are obtained at 618 K for the x = 0.6 sample. These results show that Bi doping is an effective approach for enhancing the thermoelectric properties of hexagonal Ba2-xBixCoRuO6 perovskite oxides.

Solar-driven plasmonic heterostructure Ti/TiO2-x with gradient doping for sustainable plasmon-enhanced catalysis.

Plasmon-enhanced harvesting of photons has contributed to the photochemical conversion and storage of solar energy. However, high dependence on noble metals and weak coupling in heterostructures constrain the progress towards sustainable plasmonic enhancement. Here earth-abundant Ti is studied to achieve the plasmonic enhancement of catalytic activity in a solar-driven heterostructure Ti/TiO2-x. The heterostructure was fabricated by engineering an intense coupling of a surface-etched Ti metal and a gradient-based TiO2-x dielectric via diffusion doping. Ti/TiO2-x exhibits a highly resonant light absorption band associated with surface plasmon resonances that exhibit strong near-field enhancement (NFE) and hot electron injection effects. In a photoelectrochemical system, intense interaction of the resonant plasmons with a vicinal TiO2-x dielectric accelerates the transfer of solar energy to charge carriers for plasmon-enhanced water splitting reactions. Moreover, the plasmonic Ti/TiO2-x structure presents sustained enhanced redox activities over 100 h. The intense coupling by gradient doping offers an effective approach to enable the plasmon resonances of Ti excited by visible light. The Ti-based plasmonic heterostructure potentially opens an alternative avenue towards sustainable plasmon-enhanced catalysis.

Atomic-scale insights into electro-steric substitutional chemistry of cerium oxide.

Cerium oxide (ceria, CeO2) is one of the most promising mixed ionic and electronic conducting materials. Previous atomistic analysis has widely covered the effects of substitution on oxygen vacancy migration. However, an in-depth analysis of the role of cation substitution beyond trivalent cations has rarely been explored. Here, we investigate soluble monovalent (Li+, Na+, K+, Rb+), divalent (Fe2+, Co2+, Mn2+, Mg2+, Ni2+, Zn2+, Cd2+, Ca2+, Sr2+, Ba2+), trivalent (Al3+, Fe3+, Sc3+, In3+, Lu3+, Yb3+, Y3+, Er3+, Gd3+, Eu3+, Nd3+, Pr3+, La3+) and tetravalent (Si4+, Ge4+, Ti4+, Sn4+, Hf4+, Zr4+) cation substituents. By combining classical simulations and quantum mechanical calculations, we provide an insight into defect association energies between substituent cations and oxygen vacancies as well as their effects on the diffusion mechanisms. Our simulations indicate that oxygen ionic diffusivity of subvalent cation-substituted systems follows the order Gd3+ > Ca2+ > Na+. With the same charge, a larger size mismatch with the Ce4+ cation yields a lower oxygen ionic diffusivity, i.e., Na+ > K+, Ca2+ > Ni2+, Gd3+ > Al3+. Based on these trends, we identify species that could tune the oxygen ionic diffusivity: we estimate that the optimum oxygen vacancy concentration for achieving fast oxygen ionic transport is ≈2.5% for GdxCe1-xO2-x/2, CaxCe1-xO2-x and NaxCe1-xO2-3x/2 at 800 K. Remarkably, such a concentration is not constant and shifts gradually to higher values as the temperature is increased. We find that co-substitutions can enhance the impact of the single substitutions beyond that expected by their simple addition. Furthermore, we identify preferential oxygen ion migration pathways, which illustrate the electro-steric effects of substituent cations in determining the energy barrier of oxygen ion migration. Such fundamental insights into the factors that govern the oxygen diffusion coefficient and migration energy would enable design criteria to be defined for tuning the ionic properties of the material, e.g., by co-substitutions.

Near interface ionic transport in oxygen vacancy stabilized cubic zirconium oxide thin films.

The cubic phase of pure zirconia (ZrO2) is stabilized in dense thin films through a controlled introduction of oxygen vacancies (O defects) by cold-plasma-based sputtering deposition. Here, we show that the cubic crystals present at the film/substrate interface near-region exhibit fast ionic transport, which is superior to what is obtained with similar yttrium-stabilized cubic zirconia thin films.

Tuning the Two-Dimensional Electron Liquid at Oxide Interfaces by Buffer-Layer-Engineered Redox Reactions.

Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO3 (STO) achieved using polar La7/8Sr1/8MnO3 (LSMO) buffer layers to manipulate both polarities and redox reactions from disordered overlayers grown at room temperature. Using resonant X-ray reflectometry experiments, we quantify redox reactions from oxide overlayers on STO as well as polarity induced electronic reconstruction at epitaxial LSMO/STO interfaces. The analysis reveals how these effects can be combined in a STO/LSMO/disordered film trilayer system to yield high mobility modulation doped 2DELs, where the buffer layer undergoes a partial transformation from perovskite to brownmillerite structure. This uncovered interplay between polar discontinuities and redox reactions via buffer layers provides a new approach for the design of functional oxide interfaces.

Giant Tunability of the Two-Dimensional Electron Gas at the Interface of γ-Al2O3/SrTiO3.

Two-dimensional electron gases (2DEGs) formed at the interface between two oxide insulators provide a rich platform for the next generation of electronic devices. However, their high carrier density makes it rather challenging to control the interface properties under a low electric field through a dielectric solid insulator, that is, in the configuration of conventional field-effect transistors. To surpass this long-standing limit, we used ionic liquids as the dielectric layer for electrostatic gating of oxide interfaces in an electric double layer transistor (EDLT) configuration. Herein, we reported giant tunability of the physical properties of 2DEGs at the spinel/perovskite interface of γ-Al2O3/SrTiO3 (GAO/STO). By modulating the carrier density thus the band filling with ionic-liquid gating, the system experiences a Lifshitz transition at a critical carrier density of 3.0 × 1013 cm-2, where a remarkably strong enhancement of Rashba spin-orbit interaction and an emergence of Kondo effect at low temperatures are observed. Moreover, as the carrier concentration depletes with decreasing gating voltage, the electron mobility is enhanced by more than 6 times in magnitude, leading to the observation of clear quantum oscillations. The great tunability of GAO/STO interface by EDLT gating not only shows promise for design of oxide devices with on-demand properties but also sheds new light on the electronic structure of 2DEG at the nonisostructural spinel/perovskite interface.

Enhancement of the chemical stability in confined δ-Bi2O3.

Bismuth-oxide-based materials are the building blocks for modern ferroelectrics, multiferroics, gas sensors, light photocatalysts and fuel cells. Although the cubic fluorite δ-phase of bismuth oxide (δ-Bi2O3) exhibits the highest conductivity of known solid-state oxygen ion conductors, its instability prevents use at low temperature. Here we demonstrate the possibility of stabilizing δ-Bi2O3 using highly coherent interfaces of alternating layers of Er2O3-stabilized δ-Bi2O3 and Gd2O3-doped CeO2. Remarkably, an exceptionally high chemical stability in reducing conditions and redox cycles at high temperature, usually unattainable for Bi2O3-based materials, is achieved. Even more interestingly, at low oxygen partial pressure the layered material shows anomalous high conductivity, equal or superior to pure δ-Bi2O3 in air. This suggests a strategy to design and stabilize new materials that are comprised of intrinsically unstable but high-performing component materials.

Quantization of Hall Resistance at the Metallic Interface between an Oxide Insulator and SrTiO_{3}.

The two-dimensional metal forming at the interface between an oxide insulator and SrTiO_{3} provides new opportunities for oxide electronics. However, the quantum Hall effect, one of the most fascinating effects of electrons confined in two dimensions, remains underexplored at these complex oxide heterointerfaces. Here, we report the experimental observation of quantized Hall resistance in a SrTiO_{3} heterointerface based on the modulation-doped amorphous-LaAlO_{3}/SrTiO_{3} heterostructure, which exhibits both high electron mobility exceeding 10,000 cm^{2}/V s and low carrier density on the order of ∼10^{12} cm^{-2}. Along with unambiguous Shubnikov-de Haas oscillations, the spacing of the quantized Hall resistance suggests that the interface is comprised of a single quantum well with ten parallel conducting two-dimensional sub-bands. This provides new insight into the electronic structure of conducting oxide interfaces and represents an important step towards designing and understanding advanced oxide devices.

Creation of high mobility two-dimensional electron gases via strain induced polarization at an otherwise nonpolar complex oxide interface.

The discovery of two-dimensional electron gases (2DEGs) in SrTiO3-based heterostructures provides new opportunities for nanoelectronics. Herein, we create a new type of oxide 2DEG by the epitaxial-strain-induced polarization at an otherwise nonpolar perovskite-type interface of CaZrO3/SrTiO3. Remarkably, this heterointerface is atomically sharp and exhibits a high electron mobility exceeding 60,000 cm(2) V(-1) s(-1) at low temperatures. The 2DEG carrier density exhibits a critical dependence on the film thickness, in good agreement with the polarization induced 2DEG scheme.

Post-lithiation: a way to control the ionic conductivity of solid-state thin film electrolyte.

Ionic conductivity is pivotal for solid-state battery performance. While the garnet oxide electrolyte Li7La3Zr2O12 (LLZO) boasts high ionic conductivity due to its distinct crystal structure and lithium-ion mobility, lithium loss during fabrication hampers its potential. In this study, we introduce a method that merges synthesis optimization with a post-lithiation process, enhancing LLZO's ionic conductivity. This approach compensates lithium loss with a gas-phase diffusion process, which stabilizes the cubic LLZO phase and amplifies its ionic conductivity by more than three orders of magnitude compared to electrolytes without post-lithiation. Through our comprehensive experimental procedure, we have conclusively determined that the film deposited at 700 °C and subsequently annealed at 700 °C with LiOH exhibits the highest conductivity, with a notable value of 1.11 × 10-2 S cm-1 at 200 °C. This is a significant boost compared to the as-deposited film (3.54 × 10-6 S cm-1 at 200 °C). Our findings present an additional approach to boosting lithium ion diffusion. The approach employed in this work has the potential to be applicable to films produced through other deposition methods, as it addresses the prevalent issue of lithium loss, a significant barrier to the utilization of lithium-rich thin films.

Controlled Electronic and Magnetic Landscape in Self-Assembled Complex Oxide Heterostructures.

Complex oxide heterointerfaces contain a rich playground of novel physical properties and functionalities, which give rise to emerging technologies. Among designing and controlling the functional properties of complex oxide film heterostructures, vertically aligned nanostructure (VAN) films using a self-assembling bottom-up deposition method presents great promise in terms of structural flexibility and property tunability. Here, the bottom-up self-assembly is extended to a new approach using a mixture containing a 2Dlayer-by-layer film growth, followed by a 3D VAN film growth. In this work, the two-phase nanocomposite thin films are based on LaAlO3 :LaBO3 , grown on a lattice-mismatched SrTiO3001 (001) single crystal. The 2D-to-3D transient structural assembly is primarily controlled by the composition ratio, leading to the coexistence of multiple interfacial properties, 2D electron gas, and magnetic anisotropy. This approach provides multidimensional film heterostructures which enrich the emergent phenomena for multifunctional applications.

Metallic and insulating interfaces of amorphous SrTiO3-based oxide heterostructures.

The conductance confined at the interface of complex oxide heterostructures provides new opportunities to explore nanoelectronic as well as nanoionic devices. Herein we show that metallic interfaces can be realized in SrTiO(3)-based heterostructures with various insulating overlayers of amorphous LaAlO(3), SrTiO(3), and yttria-stabilized zirconia films. On the other hand, samples of amorphous La(7/8)Sr(1/8)MnO(3) films on SrTiO(3) substrates remain insulating. The interfacial conductivity results from the formation of oxygen vacancies near the interface, suggesting that the redox reactions on the surface of SrTiO(3) substrates play an important role.

Improved High-Temperature Thermoelectric Properties of Dual-Doped Ca3Co4O9.

Layered structured Ca3Co4O9 has displayed great potential for thermoelectric (TE) renewable energy applications, as it is nontoxic and contains abundantly available constituent elements. In this work, we study the crystal structure and high-temperature TE properties of Ca3-2y Na2y Co4-y Mo y O9 (0 ≤ y ≤ 0.10) polycrystalline materials. Powder X-ray diffraction (XRD) analysis shows that all samples are single-phase samples and without any noticeable amount of the secondary phase. X-ray photoelectron spectroscopic (XPS) measurements depict the presence of a mixture of Co3+ and Co4+ valence states in these materials. The Seebeck coefficient (S) of dual-doped materials is significantly enhanced, and electrical resistivities (ρ) and thermal conductivities (κ) are decreased compared to the pristine compound. The maximum thermoelectric power factor (PF = S 2/ρ) and dimensionless figure of merit (zT) obtained for the y = 0.025 sample at 1000 K temperature are ∼3.2 × 10-4 W m-1 K-2 and 0.27, respectively. The zT value for Ca2.95Na0.05Co3.975Mo0.025O9 is about 2.5 times higher than that of the parent Ca3Co4O9 compound. These results demonstrate that dual doping of Na and Mo cations is a promising strategy for improving the high-temperature thermoelectric properties of Ca3Co4O9.

Robust Electronic Structure of Manganite-Buffered Oxide Interfaces with Extreme Mobility Enhancement.

The electronic structure as well as the mechanism underlying the high-mobility two-dimensional electron gases (2DEGs) at complex oxide interfaces remain elusive. Herein, using soft X-ray angle-resolved photoemission spectroscopy (ARPES), we present the band dispersion of metallic states at buffered LaAlO3/SrTiO3 (LAO/STO) heterointerfaces where a single-unit-cell LaMnO3 (LMO) spacer not only enhances the electron mobility but also renders the electronic structure robust toward X-ray radiation. By tracing the evolution of band dispersion, orbital occupation, and electron-phonon interaction of the interfacial 2DEG, we find unambiguous evidence that the insertion of the LMO buffer strongly suppresses both the formation of oxygen vacancies as well as the electron-phonon interaction on the STO side. The latter effect makes the buffered sample different from any other STO-based interfaces and may explain the maximum mobility enhancement achieved at buffered oxide interfaces.