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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mechanism of the Accelerated Water Formation Reaction under Interfacial Confinement

Subnanoscale spaces at the interface between weakly coupled thin films and their metal supports offer exciting opportunities for studying chemical reactions under confinement. Here, we investigated the kinetics of water formation (from hydrogen and chemisorbed oxygen) in the confined space at the interface between bilayer (BL) silica and a Ru(0001) support, compared to the reaction on the bare Ru(0001) surface. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments were carried out at different temperatures at elevated pressures of H 2 to follow the reaction kinetics. The apparent activation energy at the BL-silica/Ru(0001) interface was found to be 0.38 eV lower than that on bare Ru(0001), consistent with a recent report by Prieto et al. (Angew. Chem., Int. Ed.2018, 57(28), 8749–8753) carried out at lower H 2 pressures using low-energy electron microscopy. Density functional theory calculations revealed that the rate-limiting step in the direct hydrogenation pathway on the Ru(0001) surface is the first hydrogen addition step (*H + *O ↔ *OH). The confinement at the BL-silica/Ru(0001) interface only marginally affects the energy barrier of the first hydrogen addition. Instead, it activates an alternative disproportionation reaction pathway (*H 2 O + *O ↔ 2*OH). On the bare Ru(0001) surface, the disproportionation pathway can only occur at cryogenic temperatures or under high water vapor pressures. However, the presence of the BL-silica increases the desorption barrier for water molecules at the interface. The increased residence time allows trapped water molecules to react with chemisorbed oxygen to produce two *OH per H 2 O with an activation energy 0.25 eV lower than that of the first hydrogen addition step. Finally, this work reveals the origin of the observed accelerated water formation reaction at the BL-silica/Ru(0001) interface in the low-temperature regime (T < 350 K) and points to a route to engineer chemical reaction pathways by leveraging subnanoscale confined spaces at metal–oxide interfaces.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Marangoni effect and its potential utilization in supporting lunar habitats and other extraterrestrial endeavors

Tears of wine is a phenomenon frequently observed as a ring of wine formed near the top of the glass generates droplets that fall back into the wine. This phenomenon can be explained by the Marangoni effect driven by the surface tension created via gradient on concentration and temperature along with the interface between two phases. Besides being observed while drinking wine, the Marangoni effect is crucial for welding metals, manufacturing integrated circuits, and growing crystals; the Marangoni effect might be also crucial in supporting lunar habitats and other extraterrestrial endeavors as vacuum and reduced gravity are expected to augment the Marangoni effect on extraterrestrial molten soil leading to sustainable extraterrestrial in-situ resources utilization (ISRU). Preliminary Marangoni effect assessment on molten lunar regolith was conducted via JSC-1A lunar regolith simulant under vacuum yielding a spontaneous upwards migration of a uniform molten thin-film front that climbed the crucible wall covering the entire wall’s surface and reaching the crucible’s top end. A temperature gradient within the melt’s bulk and along the crucible’s wall generates a surface tension large enough not only to form a meniscus within the three-phase junction (crucible’s wall, bulk melt, and vacuum) but also to supersede the gravitational force to create the upwards migration of a thin film front originated on the meniscus. The observed extensive wettability of the melt with the crucible surface, an additional key factor besides surface tension necessary to sustain upwards migration, is atypical to what it has been witnessed on molten JSC-1A lunar regolith simulant under non-vacuum conditions and smaller sample sizes. The unique formation and self-migration of a thin-film front could enable key ISRU processes such as thin-film coating, crystal growth, and feedstock generation for additive 3D printing. Further assessment on the higher-temperature vacuum-driven decomposition of the uniform thin-film front as it climbed the crucible’s wall revealed a significant decomposition of various simulant’s metal-oxide components into their respective oxygen and metal elements strengthening the feasibility of extraterrestrial generation and fractional separation of oxygen and metals/alloys with none or minimal need for terrestrial precursors. The Marangoni effect assessment on molten JSC-1A lunar regolith simulant clearly opens novel pathways in future extraterrestrial ISRU endeavors including manufacturing and mining. Extraterrestrial mining will require an operational approach completely different from the terrestrial one that heavily relies on not only mechanical excavation and transportation but also post-processing; an in-situ all-in-one process might be feasible via these two coupled phenomena, self-migration and decomposition.

J A Dominguez↗
DOE OSTI2022

Angle-resolved polarimetry of hybrid perovskite emission for photonic technologies

Coupling between light and matter strongly depends on the polarization of the electromagnetic field and the nature of excitations in a material. As hybrid perovskites emerge as a promising class of materials for light-based technologies such as LEDs, LASERs, and photodetectors, it is critical to understand how their microstructure changes the intrinsic properties of the photon emission process. While the majority of optical studies have focused on the spectral content, quantum efficiency and lifetimes of emission in various hybrid perovskite thin films and nanostructures, few studies have investigated other properties of the emitted photons such as polarization and emission angle. Here, we use angle-resolved cathodoluminescence microscopy to access the full polarization state of photons emitted from large-grain hybrid perovskite films with spatial resolution well below the optical diffraction limit. In this work, mapping these Stokes parameters as a function of the angle at which the photons are emitted from the thin film surface, we reveal the effect of a grain boundary on the degree of polarization and angle at which the photons are emitted. Such studies of angle- and polarization-resolved emission at the single grain level are necessary for future development of perovskite-based flat optics, where effects of grain boundaries and interfaces need to be mitigated.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Revealing and Elucidating ALD-Derived Control of Lithium Plating Microstructure

The practical implementation of Li metal batteries is hindered by difficulties in controlling the Li metal plating microstructure. While previous atomic layer deposition (ALD) studies have focused on directly coating Li metal with thin films for the passivation of the electrode–electrolyte interface, a different approach is adopted, situating the ALD film beneath Li metal and directly on the copper current collector. Here, a mechanistic explanation for this simple strategy of controlling the Li metal plating microstructure using TiO 2 grown on copper foil by ALD is presented. In contrast to previous studies where ALD-grown layers act as artificial interphases, this TiO 2 layer resides at the copper–Li metal interface, acting as a nucleation layer to improve the Li metal plating morphology. Upon lithiation of TiO 2 , a Li x TiO 2 complex forms; this alloy provides a lithiophilic surface layer that enables uniform and reversible Li plating. The reversibility of lithium deposition is evident from the champion cell (5 nm TiO 2 ), which displays an average Coulombic efficiency (CE) of 96% after 150 cycles at a moderate current density of 1 mA cm –2 . This simple approach provides the first account of the mechanism of ALD-derived Li nucleation control and suggests new possibilities for future ALD-synthesized nucleation layers.

25 ENERGY STORAGE↗
DOE OSTI2022

Interfacial Water Manipulation with Ionic Liquids for the Oxygen Reduction Reaction

The role that interfacial water plays in both promoting and inhibiting the electrochemical oxygen reduction reaction (ORR) remains somewhat unclear and controversial. Here, we use electroanalytical chemistry, spectroscopy, and microkinetic modeling to probe the impact of hydrophobic ionic liquid (IL) thin films on interfacial water structure and its role in promoting or inhibiting the ORR. Through the use of in situ ATR-SEIRAS, we find that the IL thin films limit the content of water at the interface and prevent the formation of hydrogen bond stabilized water organization. The impact of this exclusion of water on the promotion of the ORR is through the reduced coverage of OH ad spectator species. The decreased solvation of “active” OH ad species weakens its interaction with the catalyst surface, lowering the barrier to the last step in the ORR mechanism. This “destabilized” OH ad impact on ORR kinetics is confirmed through a microkinetic model. Furthermore, the results presented here highlight the mechanistic pathway through which hydrophobic ILs enhance ORR kinetics and point to pathways to both further improve this performance enhancement and the potential for integration of hydrophobic ILs into other technologically relevant elementary electrochemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Anomalous transverse resistance in the topological superconductor β-Bi2Pd

Abstract A supercurrent flowing in a superconductor meets no resistance. Yet an electric field may still be established within the superconductor in the presence of dissipative processes, such as vortex motion. Here we report the observation of a transverse voltage drop in superconducting β- Bi 2 Pd thin films. Unlike the Hall effect in general or in other superconductors, the sign of the observed transverse voltage does not depend on the external magnetic field. Instead, it is dictated by the broken inversion symmetry on the film interfaces. This anomalous transverse voltage, or transverse resistance, is indicative of a chirality that likely resonates with the topological surface states reported in β- Bi 2 Pd.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Enhanced van der Waals epitaxy of germanium by out-of-plane dipole moment induced from transferred graphene on TiN/AlN multilayers

We report recent advances in 3D/2D heterostructures have opened up tremendous opportunities in building highly flexible and durable optoelectronic devices. However, the inherit lack of interfacial bonding and low surface energy of van der Waals surfaces limit the nucleation and growth of 3D materials. Enhancing wettability by providing a porous buffer is effective in growing compound semiconductors on graphene while van der Waals epitaxy of Ge remains challenging. Here, the nucleation of Ge has been significantly improved from an islanded mode to granular modes by using a TiN/AlN multilayered buffer prior to Ge/graphene integration. Highly textured Ge growth with dominating (111), (220), and (311) peaks are identified by x-ray diffraction. The microstructure of the buffer TiN/AlN demonstrates a polycrystalline quality with clean interfaces between each interlayer and the substrate. Kelvin probe force microscopy measurements along the lateral TiN/AlN interface identify a potential drop corresponding to the AlN phase. This contact potential difference between TiN and AlN is the key in generating the out-of-plane dipole moment that modifies the surface energy of the monolayer graphene, resulting in enhanced wettability of the Ge adatoms nucleated on top. Surface dipole induced nucleation of 3D semiconductor thin films on 2D materials via the proper design of buffer layer is fundamentally important to enhance the 3D/2D growth toward flexible optoelectronic applications.

36 MATERIALS SCIENCE↗
NASA NTRS1988

Low temperature storage container for transporting perishables to space station

This invention is directed to the long term storage of frozen and refrigerated food and biological samples by the space shuttle to the space station. A storage container is utilized which has a passive system so that fluid/thermal and electrical interfaces with the logistics module is not required. The container for storage comprises two units, each having an inner storage shell and an outer shell receiving the inner shell and spaced about it. The novelty appears to lie in the integration of thermally efficient cryogenic storage techniques with phase change materials, including the multilayer metalized surface thin plastic film insulation and the vacuum between the shells. Additionally the fiberglass constructed shells having fiberglass honeycomb portions, and the lining of the space between the shells with foil combine to form a storage container which may keep food and biological samples at very low temperatures for very long periods of time utilizing a passive system.

Dean, William G↗
DOE OSTI2025

Sequential Infiltration Synthesis (SIS) of In 2 O 3 -Based Porous Photoelectrodes for Molecular Sensitization

High-surface-area photoelectrodes are highly desirable for solar energy conversion applications, particularly in systems where surface-bound molecular chromophores are responsible for light absorption. To this end, porous Indium-Zinc-Oxide (IZO) frameworks are fabricated via Sequential Infiltration Synthesis (SIS) into poly(methyl methacrylate) (PMMA) films followed by air annealing. A more complete understanding of the multimetal infiltration process conditions and postannealing temperature allows for precise control of zinc (Zn) incorporation to afford porous, conductive, transparent, and amorphous photoelectrodes. Uniform incorporation of both indium (In) and Zn is found to require extended diethylzinc (DEZ) exposures to compensate for remarkably slow precursor diffusion in the presence of indium oxyhydroxide nuclei. SIS-fabricated IZO photoelectrodes are structurally robust, electrochemically active, and exhibit dye adsorption that suggest practical surface area enhancements greater than 100×. In conclusion, these attributes establish SIS as a rapid, scalable, and reproducible route to photoelectrodes for solar energy conversion and hybrid interface characterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Cross-Cutting Metrology Tools for In Operando Characterization of Carrier Dynamics in Photovoltaic Devices (Final Technical Report)

Understanding the nature of recombination and its dependence on defects and interfaces is essential for engineering materials and contacts for higher V oc and photovoltaic (PV) efficiency. Time-resolved photoluminescence (TRPL) has conventionally been used to evaluate recombination, but not all materials are strongly emissive or otherwise suitable. Time-resolved terahertz spectroscopy is a pump – probe method that presents valuable complementary information, wherein an optical pump pulse photoexcites carriers within the absorber and the transient photoconductivity is probed with a terahertz pulse. Until now, experimental constraints have prohibited the use of terahertz probes to interrogate full device stacks, and measurements were instead made on exfoliated films or films grown on unconventional substrates. However, interfaces are critical to the behavior of photoexcited carriers in solar cells, and the substrates themselves often influence the film growth and bulk properties. Therefore, it is important to probe the behavior of PV absorbers as close as possible to their normal operating conditions. Here we have developed cross-cutting metrology that enable in operando characterization of carrier dynamics and recombination mechanisms in working PV devices. Through a combination of complementary non-contact TRTS and TRPL experiments and modeling, we have obtained key parameters including photoexcited carrier bulk lifetime and interface and back surface recombination velocities with greater precision and accuracy than can be achieved with conventional TRPL alone. By varying pulsed photoexcitation conditions, the contributions of interface and bulk recombination mechanisms can be determined. We have developed and refined this characterization approach by investigating CdTe PVs, which is a well-established technology but with significant margin for further improvements in efficiency. Results were published in Journal of Applied Physics (DOI: 10.1063/5.0064730) and Proceedings of the IEEE PVSC (DOI: 10.1109/PVSC43889.2021.9518559). After validating the approach, we have applied it to correlate recombination rates to processing conditions and material properties, including composition and defects as well as interfaces and surface treatments. Such feedback can inform processing and design choices to enable higher PV efficiency, not only for CdTe, but also CdSe x Te 1-x , CIGS, perovskites, kesterites, and future technologies. A perspective on predicting solar cell performance from terahertz spectroscopy was published in Advanced Energy Materials (DOI: 10.1002/aenm.202102776). The cross-cutting metrology tools developed here will enable determination of the locus and mechanism of performance-limiting recombination in thin film PV devices. This feedback can guide the engineering of PV devices with higher V oc and efficiency, thereby leading to reductions in levelized cost of electricity to meet the SunShot 2030 target of $0.03/kWh for utility-scale PV. Lower costs will enable rapid expansion of renewable electricity generation that is nearly free of carbon emissions. Reducing carbon emissions of the electricity sector is one of the most important solutions to climate change. The project’s specific focus on CdTe PV can benefit First Solar, the US company that is the global leader in CdTe technology, through both technology and workforce development.

14 SOLAR ENERGY↗
DOE OSTI2025

Unveiling the Interfacial Reconstruction Mechanism Enabling Stable Growth of the Delafossite PdCoO 2 on Al 2 O 3 and LaAlO 3

Delafossites, composed of noble metal (A + ) and strongly correlated sublayers (BO 2 – ), form natural superlattices with highly anisotropic properties. These properties hold significant promise for various applications, but their exploitation hinges on the successful growth of high-quality thin films on suitable substrates. Unfortunately, the unique lattice geometry of delafossites presents a significant challenge to thin-film fabrication. Different delafossites grow differently, even when deposited on the same substrate, ranging from successful epitaxy to complete growth suppression. These variations often lack a clear correlation to obvious causes like lattice mismatch. Unidentified stabilization mechanisms appear to enable growth in certain cases, allowing these materials to form stable thin films or act as buffer layers for subsequent delafossite growth. This study employs advanced scanning transmission electron microscopy techniques to investigate the nucleation mechanism underlying the stable growth of PdCoO 2 films on Al 2 O 3 and LaAlO 3 substrates grown via molecular-beam epitaxy. Our findings reveal the presence of a secondary phase within the substrate surface that stabilizes the films. This mechanism deviates from the conventional understanding of strain relief mechanisms at oxide heterostructure interfaces and differs significantly from those observed for Cu-based delafossites.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Epitaxial Design of Complex Nickelates as Electrocatalysts for the Oxygen Evolution Reaction

Abstract The oxygen evolution reaction (OER) is a crucial process in electrochemical water splitting, a promising technology to renewably yield hydrogen gas from water. Designing and developing earth‐abundant, efficient, and stable OER electrocatalysts to replace the most widely used but scarce RuO 2 and IrO 2 are thus of critical interest. Recently, ABO 3 ‐structured perovskite oxides, especially rare‐earth nickelates, are extensively studied for their potential use as OER electrocatalysts. In particular, the epitaxial synthesis of complex oxide thin films allows flexible and precise control over the materials so that their structure–stability–property relationships can be established. Using nickelate thin films as model systems, this review illustrates how epitaxial design allows researchers to test different hypotheses and proposed descriptors, as well as formulate new design principles. Following a brief introduction to the background of OER mechanisms, proposed activity descriptors, and synthesis methods, various epitaxial design strategies are surveyed including strain tuning, composition control, surface termination/orientation selection, defect engineering, and interface design. These have led to precise control over the atomic structures and electronic properties of nickelates which in turn determine their electrochemical performance. Finally, the remaining challenges and perspectives toward a deeper understanding and use of complex oxides as OER catalysts are discussed.

Choi, Min‐Ju↗
DOE OSTI2024

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Utilizing the self-assembly of block copolymers with large Flory–Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air–polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. Here we further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Abrupt orthorhombic relaxation in compressively strained ultrathin SrRuO 3 films

Lattice structure can dictate electronic and magnetic properties of a material. Especially, reconstruction at a surface or heterointerface can create properties that are fundamentally different from those of the corresponding bulk material. In this work, we have investigated the lattice structure on the surface and in the thin films of epitaxial SrRuO 3 with the film thickness up to 22 pseudo-cubic unit cells (u.c.), using the combination of surface sensitive low energy electron diffraction and bulk sensitive scanning transmission electron microscopy. Our analysis indicates that, in contrast to many perovskite oxides, the RuO6 tilt and rotational distortions appear even in single unit cell SrRuO 3 thin films on cubic SrTiO 3 , while the full relaxation to the bulk-like orthorhombic structures takes 3-4 u.c. from the interface for thicker films. Yet the TiO 6 octahedra of the substrate near the interface with SrRuO 3 films show no sign of distortion, unlike those near the interface with CaRuO 3 films. Two orthogonal in-plane rotated structural domains are identified. These octahedral distortions are essential for the understanding of the thickness dependent transport and magnetism in ultrathin films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Solvent-Free and Non-Sintered 500 Wh/kg All Solid-State Battery

Navitas teamed up with UMD and ORNL to establish a reliable scientific research team. The project addressed processing limitations of state-of-the-art solid electrolytes by extending solvent-free electrode fabrication technology to the scalable production of cathode/solid electrolyte laminates. The innovation started with a solid-state sulfide electrolyte (LiPS) with Cl stabilization able to meet the keystone conductivity challenge in a film of practical thickness (μ 50 µm). The electrolyte was based on a composite of PTFE, and stabilized LiPSCl. With optimization, the ionic conductivity reached 3.3 ×10 -3 S/cm. The solid electrolyte with as low as 0.4% binder allowed long term cycling (> 500 cycles) of Li/SSE/Li cell at > 4 mA/cm 2 with the utilization of Li > 80%. The Li and SSE interfaces were successfully protected with LiF-rich SEI layer. NCM811cathode active materials were coated with a thin layer of Al 2 O 3 (5 nm). The free standing cathode film was fabricated through dry-process with Al2O3-coated NCM811, LiPSCl, active carbon, and small amount PTFE. The all-solid-state batteries were laminated with free standing surface coated NCM811 cathode film, free standing LiPSCl SSE film, and surface protected Li anode together in a single lamination step, and demonstrated high specific capacity (> 200 mAh/g) with coulombic efficiency > 99.5%. The all-solid-state batteries through solvent-free and no-sintering process are promising for large format cell with 500 Wh/Kg specific energy density.

25 ENERGY STORAGE↗
DOE OSTI2022

Enhanced Oxide Reduction by Hydrogen at Cuprous Oxide–Copper Interfaces near Ascending Step Edges

We report that understanding the dynamic processes involved in the interaction of hydrogen with oxides is of fundamental importance in catalysis. This paper probes the reduction of Cu 2 O-‘29’ surfaces by hydrogen at room temperature combining in situ ambient pressure scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Reduction of the atomic layer thin Cu 2 O film is observed to be preferentially initiated2 at step edges and terrace defects, where perfect Cu 2 O(111) terraces are found to be stable towards hydrogenation under the same conditions. After a long induction period, regions of partially reduced Cu 2 O-‘29’ and metallic Cu co-exist before the surface is fully reduced to Cu(111). The reduction rate strongly depends on the nature of nearby Cu step edges. We propose a mechanism for the reduction of Cu 2 O-‘29’ by hydrogen where free copper atoms from ascending metallic step edges facilitate the formation of active ensembles for H 2 dissociation and transfer H to the edges of Cu2O regions

08 HYDROGEN↗
DOE OSTI2022

Microstructure of Methylammonium Lead iodide Perovskite Thin Films: A Comprehensive Study of the Strain and Texture

Controlling the microstructure of hybrid halide perovskite thin films is essential for optimizing their performance in optoelectronic devices. It is well established that the strain state of the perovskite layer affects its stability. Likewise, the orientation of the perovskite lattice is a determining parameter as these materials have shown pronounced anisotropies in their physical and mechanical properties. In this work, the authors focus on the understanding of the mechanisms that govern the strain and texture observed in MAPbI 3 thin films deposited on various oxide substrates. A thorough study of the evolution of the strain of the perovskite layer upon cooling down to room temperature from the crystallization temperature (100 °C) shows an essentially relaxed behavior of the perovskite layers. This result contradicts the commonly accepted hypothesis according to which MAPbI 3 layers synthesized above ambient temperature are strained due to the large mismatch in the thermal expansion coefficients of the perovskite and its substrate. The texture in MAPbI 3 layers is investigated by means of synchrotron full-field diffraction X-ray microscopy. This technique allows the direct observation of the [hh0] and [00l]-oriented domains at the origin of the observed textures, demonstrating both their twin and ferroelastic nature. The stability of the different domain orientations is investigated by DFT calculations, illustrating the determining role of the chemical environment at the film-substrate interface. PbI 2- terminated surfaces are found to favor the [hh0] orientations while for MAI-terminated ones, both [hh0] and [00l] domains are equally stabilized. The different results constitute an important step of clarification and understanding from the perspective of controlling the microstructure of perovskite layers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Tunable Microwave Conductance of Nanodomains in Ferroelectric PbZr 0.2 Ti 0.8 O 3 Thin Film

Ferroelectric materials exhibit spontaneous polarization that can be switched by electric field. Beyond traditional applications as nonvolatile capacitive elements, the interplay between polarization and electronic transport in ferroelectric thin films has enabled a path to neuromorphic device applications involving resistive switching. A fundamental challenge, however, is that finite electronic conductivity may introduce considerable power dissipation and perhaps destabilize ferroelectricity itself. In this work, tunable microwave frequency electronic response of domain walls injected into ferroelectric lead zirconate titanate (PbZr 0.2 Ti 0.8 O 3 ) on the level of a single nanodomain is revealed. Tunable microwave response is detected through first-order reversal curve spectroscopy combined with scanning microwave impedance microscopy measurements taken near 3 GHz. Contributions of film interfaces to the measured AC conduction through subtractive milling, where the film exhibited improved conduction properties after removal of surface layers, are investigated. Using statistical analysis and finite element modeling, we inferred that the mechanism of tunable microwave conductance is the variable area of the domain wall in the switching volume. These observations open the possibilities for ferroelectric memristors or volatile resistive switches, localized to several tens of nanometers and operating according to well-defined dynamics under an applied field.

36 MATERIALS SCIENCE↗