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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Degradation & Performance Studies of ALD-Stabilized Nano-Composite SOFC Cathodes

This work showed, definitively, for the first time, that zirconia Atomic Layer Deposited (ALD) overcoats improve the stability of Solid Oxide Fuel Cell (SOFC) cathodes by chemically gettering interfacial Sr that has segregated out of lanthanum strontium cobalt iron oxide (LSCF). The optimum ALD ZrO 2 overcoat thickness was found to be ≥5 nm and <10 nm. Gadolinium doped ceria (GDC) pre-infiltration was also shown, for the first time, to improve SOFC cathode stability through the chemical getting of Sr at the LSCF-backbone and LSCF-gas interfaces. Due to the fact that it can be performed easily in air on large-area electrodes, GDC pre-infiltration is likely more commercially viable than ALD ZrO 2 overcoating as an interfacial Sr gettering technique. Combining ZrO 2 overcoating with GDC pre-infiltration was not successful because the GDC nano-particles gettered the ZrO 2 overcoat instead of the interfacial Sr.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Enhancing Metal‐Support Interactions of Ru Catalysts via Relaxation of Oxygen Vacancies for Hydrogen Production

The stability of Ru-based catalysts under harsh electrochemical conditions is a critical challenge limiting their practical application in energy conversion systems. In this study, Ru catalysts supported on ZrO 2-x , CeO 2-x , and ZrCeO 2-x are synthesized via pyrolysis of metal-organic frameworks (MOFs) and systematically evaluated to elucidate the role of support interactions on catalytic performance and durability. Advanced characterization techniques, including HR-TEM, XRD, XPS, and EXAFS, revealed that Ru-ZrCeO 2-x exhibited superior structural stability compared to Ru-ZrO 2-x and Ru-CeO 2-x , particularly under high-potential sweep (HPS) conditions. The incorporation of Ce into ZrO 2-x is shown to stabilize oxygen vacancies and enhance the interaction between Ru catalyst and the support, thereby mitigating catalyst degradation. Density functional theory (DFT) calculations further confirmed that Ce doping decreases formation energy of the oxygen vacancy, providing a thermodynamically favorable environment for Ru stabilization. This work demonstrates the promise of ZrCeO 2-x as a robust support material for Ru-based catalysts, advancing their potential for durable and efficient energy applications.

hydrogen evolution reaction↗
DOE OSTI2024

3D Ferroelectric Phase Field Simulations of Polycrystalline Multi‐Phase Hafnia and Zirconia Based Ultra‐Thin Films

Abstract HfO 2 – and ZrO 2 –based ferroelectric thin films have emerged as promising candidates for the gate oxides of next‐generation electronic devices. Recent work has experimentally demonstrated that a tetragonal/orthorhombic (t/o‐) phase mixture with partially in‐plane polarization can lead to negative capacitance (NC) stabilization. However, there is a discrepancy between experiments and the theoretical understanding of domain formation and domain wall motion in these multi‐phase, polycrystalline materials. Furthermore, the effect of anisotropic domain wall coupling on NC has not been studied so far. Here, 3D phase field simulations of HfO 2 – and ZrO 2 –based mixed‐phase ultra‐thin films on silicon are applied to understand the necessary and beneficial conditions for NC stabilization. It is found that smaller ferroelectric grains and a larger angle of the polar axis with respect to the out‐of‐plane direction enhances the NC effect. Furthermore, it is shown that theoretically predicted negative domain wall coupling even along only one axis prevents NC stabilization. Therefore, it is concluded that topological domain walls play a critical role in experimentally observed NC phenomena in HfO 2 – and ZrO 2 –based ferroelectrics.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Engineering lithium-ion battery cathodes for high-voltage applications using electromagnetic excitation

Microwave radiation (MWR), a type of electromagnetic excitation source, reduces the synthesis temperature and processing time for chemical reactions compared to traditional synthesis methods. Recently, we demonstrated that MWR can engineer ceramics with different crystal phases compared to traditional methods [ Journal of Materials Chemistry A 5 , 35 (2017)]. Here, we further apply the MWR-assisted technique to improve the electrochemical performance of LiCoO 2 cathodes by engineering TiO 2 and ZrO 2 ceramic coatings. Electrochemical tests suggest that the TiO 2 coating improves the rate capability of the LiCoO 2 electrode. Both TiO 2 and ZrO 2 coatings improve the high-voltage (4.5 V) cycling stability of LiCoO 2 . The capacity remaining is improved from 52.8 to 84.4% and 81.9% by the TiO 2 coating and the ZrO 2 coating, respectively, after 40 cycles. We compare these results with existing studies that apply traditional methods to engineer TiO 2 /ZrO 2 on LiCoO 2 , and find that the MWR-assisted method shows better performance improvement. X-ray photoelectron spectroscopy measurements suggest that the improved cycling stability arises from the formation of metal fluorides that protect the electrode from side reactions with electrolytes. This mechanism is further supported by the reduced Co dissolution from TiO 2 /ZrO 2 -coated LiCoO 2 electrode after cycling. This study provides a new toolbox facilitating the integration of many delicate, low melting point materials like polymers into battery electrodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO 2 hydrogenation

Herein we present a mechanistic study on the support effect (ZrO 2 and CeO 2 ) of In 2 O 3 catalysts in CO 2 hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In 2 O 3 catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O v ) formed by either H 2 -reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In 2 O 3 and the support oxide, rather than geometric factors or the difference in the particle size of In 2 O 3 . Theoretical modelling revealed that surface O v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO 2 adsorption on CeO 2 -supported or unsupported In 2 O 3 catalysts, CO 2 tends to bind strongly in a bent configuration on the O v site at the In 2 O 3 -ZrO 2 interface. The distinct CO 2 adsorption structures on different supported In 2 O 3 catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH 2 O* and methoxy (CH 3 O*). The relatively higher methanol selectivity of In 2 O 3 catalyst supported on ZrO 2 with respect to that on CeO 2 are suggested to stem from the greater energy difference (Δ$E_a$) between the parallel hydrogenation and C-O bond cleavage of HCOO*, which leads to the formation of methanol and CO, respectively. We report this study underlines the important role of metal-oxide-interface in determining the catalytic behavior of oxide-supported In 2 O 3 catalysts in CO 2 conversion.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Correlated Displacement of Dynamic Elastic Dipoles Produces Nonclassical Electrostriction in Zr-Doped Ceria

By combining experimental data with density functional theory-based ab initio molecular dynamics modeling, this work provides evidence that nonclassical electrostriction in isovalent Zr-doped ceria is due to the correlated anharmonic motion of dynamic elastic dipoles associated with multiple [ZrO 8 ]-local bonding units with a high Zr concentration (Zr 0.1 Ce 0.9 O 2 ). Introduction of 0.5 mol % trivalent or divalent codopants (Sc, Yb, La, or Ca) reduces the longitudinal electrostriction strain coefficient by more than a factor of 10, produces a 3-fold decrease in the relative dielectric permittivity, and increases the elastic modulus. Since these changes depend neither on the radius nor on the valency of the codopant, we conclude that the responsible species are charge-compensating oxygen vacancies (VO). For trivalent dopants (Do 0.005 Zr 0.1 Ce 0.895 O 1.9975 ), oxygen vacancies are present at a concentration ratio 1:40 with respect to Zr, giving, for random distribution, a characteristic interaction distance of ≤2.3 unit cells (1.2 nm). Oxygen vacancies participate in [ZrO 7 -V O ] local bonding units, disrupting the correlated dynamic displacements of the connected [ZrO 8 ]-local bonding units. Finally, such correlated motion of dynamic elastic dipoles may also explain the exponential increase in the longitudinal electrostriction strain coefficient with an increase in Zr concentration to <0.2 mole fraction and must be taken into account for further development of nonclassical electrostrictors based on Zr-doped ceria.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reactivity of a Zirconia–Copper Inverse Catalyst for CO 2 Hydrogenation

Copper–zirconia catalysts have been shown to be effective for methanol synthesis via CO 2 hydrogenation, yet the active phases and reaction mechanism remain uncertain. Here, an inverse model catalyst ZrO 2 /CuO 2 /Cu(111) was prepared by mass-selected ion deposition and tested for CO 2 hydrogenation under near-ambient pressure (AP) reaction conditions by using X-ray photoelectron spectroscopy (NAP-XPS) and infrared reflection–absorption spectroscopy (NAP-IRAS). The spatial resolution afforded by the small entrance cone of the AP-XPS spectrometer was used to resolve regions of the surface with and without Zr deposition. Carbon 1s core level spectra of the ZrO 2 /Cu 2 O/Cu(111) regions of the surface under 500 mTorr of CO 2 + H 2 (1:3 ratio) show evidence for reaction intermediates including carbonate (CO 3 *), formate (HCOO*), and H x CO* species, with methoxy having the highest surface concentration at 500–600 K. These intermediates are confirmed by IRAS vibrational spectra. In regions of the surface without Zr, the Cu 2 O/Cu(111) is reduced to metallic Cu, and the surface intermediates are different and are present at much lower concentrations. The observed surface intermediates and their temperature dependence suggest a mechanism in which CO 2 is adsorbed on zirconia as carbonate (CO 3 *) and then converted to HCOO* and H x CO* hydrogenated intermediates that ultimately lead to methoxy (CH 3 O*), the final surface-bound precursor for methanol. Overall, the results clearly demonstrate the promotional effects of small ZrO 2 particles for enhancing the reactivity of Cu surfaces for CO 2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Node-Solution Microenvironment Governs the Selectivity of Thioanisole Oxidation within Catalytic Zr-Based Metal–Organic Framework

Lewis acidic metal oxides, including zirconia (ZrO 2 ), are catalytically active toward oxidative reactions in the presence of sacrificial oxidants like t-butyl hydroperoxide (TBHP). The structural ambiguity and heterogeneity of the ZrO 2 surface impose challenges to chemists in understanding the reaction mechanism down to atomic-level precision. The inorganic, Zr-oxo nodes of many crystalline metal–organic frameworks (MOFs) structurally mimic ZrO 2 . Herein, we report three novel findings: (A) Zr-based MOF, Zr-MOF-808 is catalytically competent in activating TBHP to induce oxygen atom transfer (OAT) reactions to a model substrate, thioanisole, at room temperature, (B) its reaction mechanism can be derived with greater structural precision owing to the crystallinity of the MOF, and (C) the node-binding agent and other reaction conditions significantly impact the selectivity between the singly oxidized methyl phenyl sulfoxide vs the doubly oxidized sulfone. These findings suggest that both the activity and selectivity of OAT reactions within Zr-MOF-808 are governed by the chemistry occurring at the interface of the node and the surrounding reaction medium. Implications of these findings in OAT reactions and other MOF/metal oxide-catalyzed relevant catalysis are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Catalytic Reduction of Esters over Zirconia-Supported Metal Catalysts

Esters are often produced as unwanted byproducts during the catalytic upgrading of ethanol to diesel fuel precursors through Guerbet coupling. Removal of esters from the product stream is important to prevent the loss of downstream catalyst activity from ester-derived carboxylic acids. In this work, we studied ester hydrogenolysis to the parent alcohols as a viable route for enhanced diesel fuel production. Specifically, we investigated the reduction of hexyl acetate in butanol over ZrO 2 -supported Ni, Co, Cu, Rh, Pd, and Pt catalysts, where Cu/ZrO 2 was the most selective catalyst for the hydrogenolysis of hexyl acetate into hexanol and ethanol. Thermodynamic analysis reveals that a 90% alcohol yield can be obtained at 200 °C, 30 bar, and a relatively high H 2 :hexyl acetate molar ratio of 480:1. Experimentally, an alcohol yield of 88% yield was obtained with a 10 wt % Cu/ZrO 2 catalyst at these conditions with a residence time of 5.4 h kg cat kmol gas –1 . Catalytic tests on the support revealed that ZrO 2 catalyzes the transesterification reaction between hexyl acetate and butanol. However, only the Cu sites can catalyze the hydrogenolysis of the esters into the final alcohols. We developed a kinetic model for our experimental results, which shows that the transesterification and hydrogenolysis reactions run at two different timescales, the former being 10 times faster than the latter. Data regression has been used to develop a model to predict the mole fraction distribution of ester hydrogenolysis products over a wide range of contact times. Cu/ZrO 2 loses half its catalytic activity after 80 h of time on stream. Modeling of deactivation data reveals that the ZrO 2 support conserves a residual activity due to external active sites, while active sites over the Cu surface deactivate at different rates. Furthermore, the catalytic conversion of esters into their parent alcohols is relevant to the production of surrogate liquid fuels since alcohols can be bimolecularly dehydrated to produce a blend of ethers with diesel fuel-like properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Direct Optical Lithography of Colloidal Metal Oxide Nanomaterials for Diffractive Optical Elements with 2π Phase Control

Spatially patterned dielectric materials are ubiquitous in electronic, photonic, and optoelectronic devices. These patterns are typically made by subtractive or additive approaches utilizing vapor-phase reagents. On the other hand, recent advances in solution-phase synthesis of oxide nanomaterials have unlocked a materials library with greater compositional, microstructural, and interfacial tunability. However, methods to pattern and integrate these nanomaterials in real-world devices are less established. In this work, we directly optically pattern oxide nanoparticles (NPs) by mixing them with photosensitive diazo-2-naphthol-4-sulfonic acid and irradiating with widely available 405 nm light. We demonstrate the direct optical lithography of ZrO 2 , TiO 2 , HfO 2 , and ITO NPs and investigate the chemical and physical changes responsible for this photoinduced decrease in solubility. Micron-thick layers of amorphous ZrO 2 NPs were patterned with micron resolution and shown to allow 2 pi phase control of visible light. We also show multilayer patterning and use it to fabricate features with different thicknesses and distinct structural colors. Upon annealing at 400 degrees C, the deposited ZrO 2 structures have excellent optical transparency across a wide wavelength range (0.3-10 mu m), a high refractive index (n = 1.84 at 633 nm), and are optically smooth. We then fabricate diffractive optical elements, such as binary phase diffraction gratings, that show efficient diffractive behavior and good thermal stability. Different oxide NPs can also be mixed prior to patterning, providing a high level of material tunability. This work demonstrates a general patterning approach that harnesses the processability and diversity of colloidal oxide nanomaterials for use in photonic applications.

2𝜋 phase shift↗
DOE OSTI2020

Rapid assessment of structural and compositional changes during early stages of zirconium alloy oxidation

A multimodal chemical imaging approach has been developed and applied to detail the dynamic, atomic-scale changes associated with oxidation of a zirconium alloy (Zircaloy-4). Scanning transmission electron microscopy, a gas-phase reactor chamber attached to an atom probe tomography instrument, and synchrotron-based X-ray absorption near-edge spectroscopy were employed to reveal morphology, composition, crystal, and electronic structure changes that occur during initial stages of oxidation at 300 °C. Oxidation was carried out in 10 mbar O 2 gas for short exposure times of 1 and 5 min. A multilayered oxide film with a cubic ZrO adjacent to the oxide/metal interface, a nanoscopic transition region with a graded composition of ZrO 2-x (where 0 < x < 1), and tetragonal ZrO 2 in the outermost oxide were formed. Partitioning of the major alloying element (tin) to the oxide/metal interface and heterogeneously within the oxide accompanied the development of the layered oxide. Our work provides a rapid, high-throughput approach for detailed characterisation of initial stages of zirconium alloy oxidation at an accelerated time scale, with implications for several other alloy systems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Giant energy storage and power density negative capacitance superlattices

Dielectric electrostatic capacitors, because of their ultrafast charge-discharge, are desirable for high-power energy storage applications. Along with ultrafast operation, on-chip integration can enable miniaturized energy storage devices for emerging autonomous microelectronics and microsystems. Moreover, state-of-the-art miniaturized electrochemical energy storage systems-microsupercapacitors and microbatteries-currently face safety, packaging, materials and microfabrication challenges preventing on-chip technological readiness, leaving an opportunity for electrostatic microcapacitors. Here, in this study, we report record-high electrostatic energy storage density (ESD) and power density, to our knowledge, in HfO 2 -ZrO 2 -based thin film microcapacitors integrated into silicon, through a three-pronged approach. First, to increase intrinsic energy storage, atomic-layer-deposited antiferroelectric HfO 2 -ZrO 2 films are engineered near a field-driven ferroelectric phase transition to exhibit amplified charge storage by the negative capacitance effect, which enhances volumetric ESD beyond the best-known back-end-of-the-line-compatible dielectrics (115 J cm -3 ). Second, to increase total energy storage, antiferroelectric superlattice engineering scales the energy storage performance beyond the conventional thickness limitations of HfO 2 -ZrO 2 -based (anti)ferroelectricity (100-nm regime). Third, to increase the storage per footprint, the superlattices are conformally integrated into three-dimensional capacitors, which boosts the areal ESD nine times and the areal power density 170 times that of the best-known electrostatic capacitors: 80 mJ cm -2 and 300 kW cm -2 , respectively. This simultaneous demonstration of ultrahigh energy density and power density overcomes the traditional capacity-speed trade-off across the electrostatic-electrochemical energy storage hierarchy. Furthermore, the integration of ultrahigh-density and ultrafast-charging thin films within a back-end-of-the-line-compatible process enables monolithic integration of on-chip microcapacitors, which can unlock substantial energy storage and power delivery performance for electronic microsystems.

25 ENERGY STORAGE↗
DOE OSTI2020

Atomically dispersed palladium catalyses Suzuki–Miyaura reactions under phosphine-free conditions

Single-atom catalysts have emerged as a new frontier in catalysis science. However, their applications are still limited to small molecule activations in the gas phase, the classic organic transformations catalyzed by single-atom catalysts are still rare. Here, we report the use of a single-atom Pd catalyst for the classic Suzuki–Miyaura carbon–carbon coupling reaction under phosphine-free and open-air conditions at room temperature. The single-atom Pd catalyst is prepared through anchoring Pd on bimetal oxides (Pd-ZnO-ZrO 2 ). The significant synergetic effect of ZnO and ZrO 2 is observed. The catalyst exhibits high activity and tolerance of a wide scope of substrates. Characterization demonstrates that Pd single atoms are coordinated with two oxygen atoms in Pd-ZnO-ZrO 2 catalyst. The catalyst can be fabricated on a multi-gram scale using a simple in situ co-precipitation method, which endows this catalytic system with great potential in practical applications.

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

Reactivity of Pd–MO 2 encapsulated catalytic systems for CO oxidation

In this work, we present an investigation aimed at characterizing and understanding the synergistic interactions in encapsulated catalytic structures between the metal core (i.e., Pd) and oxide shell (i.e., TiO 2 , ZrO 2 , and CeO 2 ). Encapsulated catalysts were synthesized using a two-step procedure involving the initial colloidal synthesis of Pd nanoparticles (NPs) capped by various ligands and subsequent sol–gel encapsulation of the NPs with porous MO 2 (M = Ti, Zr, Ce) shells. The encapsulated catalytic systems displayed higher activity than the Pd/MO 2 supported structures due to unique physicochemical properties at the Pd–MO 2 interface. Pd@ZrO 2 exhibited the highest catalytic activity for CO oxidation. Results also suggested that the active sites in Pd encapsulated by an amorphous ZrO 2 shell structure were significantly more active than the crystalline oxide encapsulated structures at low temperatures. Furthermore, CO DRIFTS studies showed that Pd redispersion occurred under CO oxidation reaction conditions and as a function of the oxide shell composition, being observed in Pd@TiO 2 systems only, with potential formation of smaller NPs and oxide-supported Pd clusters after reaction. This investigation demonstrated that metal oxide composition and (in some cases) crystallinity play major roles in catalyst activity for encapsulated catalytic systems.

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

Atomic layer deposition of lithium zirconium oxides for the improved performance of lithium-ion batteries

Recently there has been increasing interest to develop lithium-containing films as solid-state electrolytes or surface coatings for lithium-ion batteries (LIBs) and related systems. Here, in this study, we for the first time investigated the thin film growth of lithium zirconium oxides (Li x Zr y O or LZOs) through combining two individual atomic layer deposition (ALD) processes of ZrO 2 and LiOH, i.e., sub-ALD of ZrO 2 and LiOH. We revealed that the hygroscopic nature of the LiOH component has a big impact on the growth of LZOs. We found that an increased temperature to 225 °C was more effective than an elongated purge to mitigate the adverse effects of physisorbed H 2 O. We further discovered that, during the resultant LZO super-ALD processes, the growth of sub-ALD LiOH has been promoted while the growth of sub-ALD ZrO 2 has been inhibited. In this study, a suite of instruments has been applied to characterize the LZO super-ALD processes and the resultant LZO films, including in situ quartz crystal microbalance (QCM), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), atomic force microscopy (AFM), synchrotron-based X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Furthermore, we applied the resulting LZO films over LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathodes in LIBs and demonstrated that the LZO coating films could evidently improve the lithium-ion insertion and extraction rates of the NMC622 electrodes up to 3.4 and 2.6 times, respectively. The LZO-coated NMC622 cathodes exhibited much better performance than the uncoated NMC622 ones.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Compositional and phase dependence of elastic modulus of crystalline and amorphous Hf 1- x Zr x O 2 thin films

The elastic moduli of amorphous and crystalline atomic layer-deposited Hf 1-x Zr x O 2 (HZO, x = 0, 0.31, 0.46, 0.79, 1) films prepared with TaN electrodes on silicon substrates were investigated using picosecond acoustic measurements. The moduli of the amorphous films were observed to increase between 211 ± 6 GPa for pure HfO 2 and 302 ± 9 GPa for pure ZrO 2 . In the crystalline films, it was found that the moduli increased upon increasing the zirconium composition from 248 ± 6 GPa for monoclinic HfO 2 to 267 ± 9 GPa for tetragonal ZrO 2 . Positive deviations from this increase were observed for the Hf 0.69 Zr 0.31 O 2 and Hf 0.54 Zr 0.46 O 2 compositions, which were measured to have moduli of 264 ± 8 GPa and 274 ± 8 GPa, respectively. These two compositions contained the largest fractions of the ferroelectric orthorhombic phase, as assessed from polarization and diffraction data. The biaxial stress states of the crystalline films were characterized through sin 2 (ψ) x-ray diffraction analysis. The in-plane stresses were all found to be tensile and observed to increase with the increasing zirconium composition, between 2.54 ± 0.6 GPa for pure HfO 2 and 5.22 ± 0.5 GPa for pure ZrO 2 . The stresses are consistent with large thermal expansion mismatches between the HZO films and silicon substrates. Furthermore, these results demonstrate a device-scale means to quantify biaxial stress for investigation on its effect on the ferroelectric properties of hafnia-based materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Local orthorhombic phase in zirconium oxide nanocrystals: insights from X-ray pair distribution function analysis

Zirconium dioxide (ZrO 2 ) and hafnium dioxide (HfO 2 ) have emerged as promising alternatives to conventional ferroelectric materials. Understanding the crystal phases of these oxides under different conditions is crucial for optimizing their properties. There are several theories for the (anti)ferroelectric properties; however, comprehensive analysis, particularly at the local structure level, is lacking. In this study, we investigate the local structure of ZrO 2 nanocrystals using X-ray pair distribution function (PDF) analysis, revealing an unexpected local orthorhombic distortion irrespective of crystallite size. This finding suggests the potential existence of an intermediate orthorhombic phase during the microscopic switching pathway observed in previous studies. Additionally, we explore the influence of crystallite size and surface effects on the PDF. These results contribute to a deeper understanding of the structural dynamics in ZrO 2 and offer insights for the design of next-generation ferroelectric materials.

Pokratath, Rohan (ORCID:0000000268383939)↗
DOE OSTI2023

Vertical nanoscale strain-induced electronic localization in epitaxial La2/3Sr1/3MnO3 films with ZrO2 nanopillar inclusions

Abstract Unusual electrical transport properties associated with weak or strong localization are sometimes found in disordered electronic materials. Here, we report experimental observation of a crossover of electronic behavior from weak localization to enhanced weak localization due to the spatial influence of disorder induced by ZrO 2 nanopillars in (La 2/3 Sr 1/3 MnO 3 ) 1− x :(ZrO 2 ) x ( x = 0, 0.2, and 0.3) nanocomposite films. The spatial strain regions, identified by scanning transmission electron microscopy and high-resolution x-ray diffraction, induce a coexistence of two-dimentional (2D) and three-dimentional (3D) localization and switches to typical 2D localization with increasing density of ZrO 2 pillars due to length scale confinement, which interestingly accords with enhancing vertically interfacial strain. Based on the excellent agreement of our experimental results with one-parameter scaling theory of localization, the enhanced weak localization exists in metal range close to the fixed point. These films provide a tunable experimental model for studying localization in particular the transition regime by appropriate choice of the second epitaxial phase. Graphical Abstract

36 MATERIALS SCIENCE↗