Controlling properties of functional oxides by tuning oxygen defect chemistry

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2018.Cataloged from PDF version of thesis.Includes bibliographical references (pages 164-192).Oxygen defects are essential building blocks for properties and functionalities of oxides, including electrical conductivity, magnetism, ferroelectricity as well as catalytic and electrocatalytic activity. Therefore, fundamental understanding of how to tune the oxygen defect chemistry is essential for advancing applications based on these defect sensitive properties. This thesis investigated pathways to controlling the concentration and structure of oxygen defects on selected case studies with model oxide systems. Three novel effects were assessed and shown to be operative for obtaining a large impact on the oxygen defect chemistry equilibria. These are heterogeneous chemical doping of the surface for improving surface electrocatalytic activity and stability, electrochemical bias to control phase with drastic changes obtained in electronic and phonon transport properties, as well as strain engineering to alter the oxygen interstitial capacity and oxygen exchange kinetics. Surface chemical modifications were applied to the near-surface regions of Lao.8Sro.2CoO 3 (LSC) by replacing the Co cations locally with less reducible cations, such as Hf and Ti. This strategy was shown to effectively stabilize the LSC surfaces and suppress surface segregation of Sr at elevated temperatures. This introduced surface stability by local chemical doping greatly enhanced the long-term electrochemical performance of LSC electrode, which provides a new route for improving the efficiency of solid oxide fuel and electrolysis cells. Applying electrical bias was investigated as another effective method to tune the oxygen stoichiometry, exemplified by the case studies on SrCoOx (SCO). In situ X-ray diffraction was used to investigate the topotactic phase transition between brownmillerite phase SrCoO2.5 (BM-SCO) and perovskite phase SrCoO 3 6 (P-SCO) triggered electrochemically at elevated temperatures. An electrical bias of merely 30 mV was shown sufficient to trigger the BM-->P phase transition. This is much more feasible than chemically induced phase transition, which requires high pressure (> 1 bar) and specialized pressurized apparatus. Moreover, the evolution of electronic structure during the BM4P phase transition was probed in operando by using ambient-pressure X-ray photoelectron and absorption spectroscopy (AP-XPS/XAS). The similar experimental scheme, which combines in operando surface characterizations and electrochemical controlling of oxygen stoichiometry, was extended to oxide systems beyond perovskites. This allows us to investigate the defect chemistry of oxides in a much broader range of effective oxygen partial pressure than what conventional methods can achieve. Firstly, we showed that the surface defect chemistry equilibrium of fluoritestructured Pro.iCeo.902-6 (PCO) strongly deviated from the bulk counterpart, due to the possibly enhanced defect-defect interactions or lattice strain effect at surfaces. Secondly, we found a novel metal-insulator transition triggered electrochemically in VO, by changing the phase between the metallic dioxide VO2 and the insulating pentoxide V2O5 Lastly, we lowered the operation temperature of this electrochemical control of oxygen stoichiometry down to room temperature by using ionic liquid or ion gels as the electrolyte. We achieved tuning of thermal conductivity in SrCoOx with a range of more than one order of magnitude, by using electrochemically triggered phase transitions at room temperature. We also investigated the effect of lattice strain on oxygen defect formation energy in Ruddlesden-Popper (RP) phase oxide Nd2NiO4+6 (NNO). We found that tensile strain along the c-axis of NNO lattice effectively reduced the formation enthalpy of oxygen interstitials, which can provide a new route for designing the defect chemistry of RP phase oxide for electrocatalytic applications..by Qiyang Lu.Ph. D

Surface Chemistry and Non-Stoichiometry of Nd2NiO4+ Epitaxial Thin Films with Different Orientation and Strain

The influence of lattice strain on non-stoichiometry and surface chemical composition was investigated for epitaxial Nd2NiO4+ä (NNO) films during annealing in ultra high vacuum (below 10[superscript -8] mbar) and temperatures of up to 700oC. (100)- and (001)-oriented films with tensile and compressive lattice strain along c-axis were fabricated using pulsed laser deposition method. A significant decrease in the c-lattice parameter during annealing was found by x-ray diffraction (XRD) for the tensile strained films. X-ray photoelectron spectroscopy (XPS) showed that Ni reduction during annealing takes place only in compressively strained films, indicating the lower content of oxygen interstitials. A lower interstitial content in the compressively strained NNO films is consistent with the smaller c-lattice parameter measured by XRD and the easier reducibility of Ni measured by XPS. Cation segregation and morphological changes were found only for the compressively strained film surfaces. These results show that lattice strain along the c-axis is an important parameter that can alter the surface chemistry, and thus the oxygen exchange kinetics, on Nd2NiO4+ä at elevated temperatures.National Science Foundation (U.S.) (Division of Materials Research, Ceramics Program, CAREER award

Integration of Metabolomics and Transcriptomics Reveals the Therapeutic Mechanism Underlying Paeoniflorin for the Treatment of Allergic Asthma

Objectives: Asthma is a chronic airway inflammatory disease, which is characterized by airway remodeling, hyperreactivity and shortness of breath. Paeoniflorin is one of the major active ingredients in Chinese peony, which exerts anti-inflammatory and immune-regulatory effects in multiple diseases. However, it remains unclear whether paeoniflorin treatment can suppress allergic asthma.Methods: In this study, we evaluated the effect of paeoniflorin on lung function and airway inflammation in asthmatic mice. These asthmatic Balb/c mice were first sensitized and constructed through ovalbumin (OVA) motivation. Subsequently, we determined the mechanism of action of paeoniflorin in treating allergic asthma through integrated transcriptomic and metabolomic data sets.Results: Our results demonstrated that many genes and metabolites were regulated in the paeoniflorin-treated mice. Moreover, the potential target proteins of paeoniflorin played important roles in fatty acid metabolism, inflammatory response, oxidative stress and local adhesion.Conclusion: Paeoniflorin has a beneficial effect on asthma, which may be achieved through regulating fatty acid metabolism, inflammatory response and the adhesion pathway at system level

Resistive Switching Mechanisms on TaOx and SrRuO3 Thin-Film Surfaces Probed by Scanning Tunneling Microscopy

The local electronic properties of tantalum oxide (TaO[subscript x], 2 ≤ x ≤ 2.5) and strontium ruthenate (SrRuO[subscript 3]) thin-film surfaces were studied under the influence of electric fields induced by a scanning tunneling microscope (STM) tip. The switching between different redox states in both oxides is achieved without the need for physical electrical contact by controlling the magnitude and polarity of the applied voltage between the STM tip and the sample surface. We demonstrate for TaO[subscript x] films that two switching mechanisms operate. Reduced tantalum oxide shows resistive switching due to the formation of metallic Ta, but partial oxidation of the samples changes the switching mechanism to one mediated mainly by oxygen vacancies. For SrRuO[subscript 3], we found that the switching mechanism depends on the polarity of the applied voltage and involves formation, annihilation, and migration of oxygen vacancies. Although TaO[subscript x] and SrRuO[subscript 3] differ significantly in their electronic and structural properties, the resistive switching mechanisms could be elaborated based on STM measurements, proving the general capability of this method for studying resistive switching phenomena in different classes of transition metal oxides.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Grant DMR-1419807

Chemomechanics of ionically conductive ceramics for electrical energy conversion and storage

Functional materials for energy conversion and storage exhibit strong coupling between electrochemistry and mechanics. For example, ceramics developed as electrodes for both solid oxide fuel cells and batteries exhibit cyclic volumetric expansion upon reversible ion transport. Such chemomechanical coupling is typically far from thermodynamic equilibrium, and thus is challenging to quantify experimentally and computationally. In situ measurements and atomistic simulations are under rapid development to explore how this coupling can be used to potentially improve both device performance and durability. Here, we review the commonalities of coupling between electrochemical and mechanical states in fuel cell and battery materials, illustrating with specific cases the progress in materials processing, in situ characterization, and computational modeling and simulation. We also highlight outstanding questions and opportunities in these applications – both to better understand the limiting mechanisms within the materials and to significantly advance the durability and predictability of device performance required for renewable energy conversion and storage.United States. Dept. of Energy (Basic Energy Sciences Division of Materials Sciences and Engineering, grant DE-SC0002633)United States. Dept. of Energy (Office of Science, Graduate Fellowship Program (DOE SCGF))United States. American Recovery and Reinvestment Act of 2009 (ORISE-ORAU, contract no. DE-AC05-06OR23100))United States. Dept. of Energy. Division of Materials Sciences and Engineering (MIT/DMSE Salapatas Fellowship)United States. Air Force Office of Scientific Research (Presidential Early Career Award in Science and Engineering (PECASE)

A robust and active hybrid catalyst for facile oxygen reduction in solid oxide fuel cells

The sluggish oxygen reduction reaction (ORR) greatly reduces the energy efficiency of solid oxide fuel cells (SOFCs). Here we report our findings in dramatically enhancing the ORR kinetics and durability of the state-of-the-art La[subscript 0.6]Sr[subscript 0.4]Co[subscript 0.2]Fe[subscript 0.8]O[subscript 3](LSCF) cathode using a hybrid catalyst coating composed of a conformal PrNi[subscript 0.5]Mn[subscript 0.5]O[subscript 3](PNM) thin film with exsoluted PrOxnanoparticles. At 750°C, the hybrid catalyst-coated LSCF cathode shows a polarization resistance of ∼0.022 Ω cm[superscript 2], about 1/6 of that for a bare LSCF cathode (∼0.134 Ω cm[superscript 2]). Further, anode-supported cells with the hybrid catalyst-coated LSCF cathode demonstrate remarkable peak power densities (∼1.21 W cm[superscript -2]) while maintaining excellent durability (0.7 V for ∼500 h). Near Ambient X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-Ray Absorption Fine Structure (NEXAFS) analyses, together with density functional theory (DFT) calculations, indicate that the oxygen-vacancy-rich surfaces of the PrOxnanoparticles greatly accelerate the rate of electron transfer in the ORR whereas the thin PNM film facilitates rapid oxide-ion transport while drastically enhancing the surface stability of the LSCF electrode

Self-Arranged Misfit Dislocation Network Formation upon Strain Release in La0.7Sr0.3MnO3/LaAlO3(100) Epitaxial Films under Compressive Strain

Lattice-mismatched epitaxial films of LaSrMnO (LSMO) on LaAlO (001) substrates develop a crossed pattern of misfit dislocations above a critical thickness of 2.5 nm. Upon film thickness increases, the dislocation density progressively increases, and the dislocation spacing distribution becomes narrower. At a film thickness of 7.0 nm, the misfit dislocation density is close to the saturation for full relaxation. The misfit dislocation arrangement produces a 2D lateral periodic structure modulation (Λ≈ 16 nm) alternating two differentiated phases: one phase fully coherent with the substrate and a fully relaxed phase. This modulation is confined to the interface region between film and substrate. This phase separation is clearly identified by X-ray diffraction and further proven in the macroscopic resistivity measurements as a combination of two transition temperatures (with low and high T). Films thicker than 7.0 nm show progressive relaxation, and their macroscopic resistivity becomes similar than that of the bulk material. Therefore, this study identifies the growth conditions and thickness ranges that facilitate the formation of laterally modulated nanocomposites with functional properties notably different from those of fully coherent or fully relaxed material

Spatiotemporal variations and risk characteristics of potential non-point source pollution driven by LUCC in the Loess Plateau Region, China

With increasing human activities, regional substrate conditions have undergone significant changes. These changes have resulted in temporal and spatial variations of non-point source pollution sources, which has a significant impact on the quality of the regional soil, surface water, and groundwater environments. This study focused on the human-disturbed Loess Plateau region and used an enhanced potential non-point-source pollution index (PNPI) model to explore the dynamic changes of regional potential non-point-source pollution (PNP) and the associated risk due to land use and land cover change (LUCC) over the past 31 years. The Loess Plateau region is mainly composed of cultivated land, grassland and forest, which together account for 93.5% of the watershed area. From 1990 to 2020, extensive soil and water conservation measures were implemented throughout the Loess Plateau region, resulting in a significant reduction in the non-point source pollution risk. Using the quantile classification method, the study area’s PNP risk values were categorized into five distinct levels. The results revealed a polarization phenomenon of PNP risk in the region, with an increase in non-point source pollution risk in the human-influenced areas and a rapid expansion of the very high-risk area. However, the non-point source pollution risk in the upstream water source area of the watershed reduced over the study period. In recent years, the rapid urbanization of the Loess Plateau region has been the primary reason for the rapid expansion of the very high PNP risk area throughout the watershed. This study highlights the significant impact of LUCC on the dynamic changes in PNP risk within the Loess Plateau region, providing crucial insights into future conservation and urban planning policies aimed at enhancing the ecological health and environmental quality of the region

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss

Pushing the detection of cation nonstoichiometry to the limit

Nanoscale complex-oxide thin films prepared by well-established growth techniques, such as pulsed-laser deposition or molecular-beam epitaxy, often exhibit compositions that deviate from the ideal stoichiometry. Even small variations in composition can lead to substantial changes in the technologically relevant electronic, magnetic, and optical properties of these materials. To assess the reasons behind this variability, and ultimately to allow tuning the properties of oxide films with precise control of the deposition parameters, high-resolution detection of the nonstoichiometry introduced during growth is needed. The resolution of current techniques, such as x-ray diffraction, fluorescence, or spectroscopy, is limited to estimating composition differences in the percent level, which is often insufficient for electronic-device quality. We develop an unconventional approach based on scanning tunneling microscopy for enabling the determination of cation imbalance introduced in thin films with exceptionally small detection limit. We take advantage of the well-controlled surface reconstructions on SrTiO3(110), and use the established relation between those reconstructions and the surface composition to assess the cation excess deposited in pulsed-laser grown SrTiO3(110) films. We demonstrate that a <0.1% change in cation nonstoichiometry is detectable by our approach. Furthermore, we show that, for thin films that accommodate all the nonstoichiometry at the surface, this method has no fundamental detection limit.NSF CAREER Award of the National Science Foundation, Division of Materials Research, Ceramics Program, Grant No. 1055583U. S. National Science Foundation, Division of Materials Research (Grant no. 1419807