Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “oxide interfaces”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Corrosion and Mechanical Performance of Grade 92 Ferritic-Martensitic Steel After Exposure to Supercritical Carbon Dioxide

Grade 92 ferritic-martensitic steel is a candidate alloy for medium temperature (< 550 °C) components for the supercritical carbon dioxide (s-CO 2 ) Brayton cycle. 1000 hours exposures were performed on base and welded material in s-CO 2 at temperatures of 450 °C or 550 °C and compared to samples aged in Ar at 550 °C. Both s-CO 2 exposures resulted in a duplex oxide growth and carburization, with 450 °C exhibiting carburization in a power law diffusion profile up to a depth of 200-250 µm, while 550 °C showed a linear profile up to a depth of 100 µm. The different profiles indicate much slower precipitation and coarsening of carbides at the lower temperature, allowing carbon to diffuse deeper into the material. However, 450 °C produced improved mechanical properties while 550 °C produced deteriorated properties. This was due to the higher density of carbon near the metal–oxide interface which leads to significant carbide coarsening and, subsequently, crack initiation and early failure. Finally, additional exposure at 450 °C is predicted to increase deposited carbon, but further study would be needed to understand if and when carburization will produce a negative mechanical effect.

36 MATERIALS SCIENCE↗
DOE OSTI2026

From bulk to surface: Structure and dynamics of amorphous alumina from deep potential molecular dynamics

Understanding the atomic-scale structure and dynamics of amorphous oxide surfaces is essential for interpreting their chemical reactivity, mechanical stability, and interfacial behavior, yet direct experimental characterization remains challenging. We employ Deep Potential (DP) molecular dynamics to generate large-scale, ab initio -quality models of amorphous Al 2 O 3 bulk glasses and melt-quenched free surfaces, enabling a quantitative analysis of both structure and relaxation dynamics with statistical confidence inaccessible to direct ab initio simulation. The trained DP model reproduces experimental liquid and glass structure, captures the cooling-rate dependence of the bulk glass transition, and corrects systematic biases in the polyhedral populations predicted by widely used classical force fields. At the free surface, mass density recovers to bulk values over ~10 Å, while local coordination requires a slightly wider subsurface region to fully converge. The outermost layer is oxygen-enriched, exhibits altered polyhedral connectivity with contracted Al–O bonds, and hosts a broad population of under-coordinated motifs (notably AlO 3 and OAl 2 ) whose abundances are governed by glass stability. These under-coordinated surface motifs exhibit distinct vibrational signatures and occur as locally paired Lewis acid and Brønsted base sites consistent with bond-valence compensation, yet remain spatially dispersed rather than aggregating into extended clusters. Despite this pronounced structural heterogeneity, surface relaxation and the glass-transition temperature remain comparable to their bulk counterparts, suggesting that the disordered surface is kinetically stable once formed. Together, these results establish a molecular-level picture of amorphous alumina surfaces and demonstrate the capability of machine-learned potentials to resolve structure–property relationships in disordered oxide interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Surface properties and dye loading behavior of Zn{sub 2}SnO{sub 4} nanoparticles hydrothermally synthesized using different mineralizers

We present for the first time the influence of different mineralizers on the isoelectric point (IEP) of zinc stannate (Zn{sub 2}SnO{sub 4}) nanoparticles hydrothermally prepared using three different mineralizers, viz., Na{sub 2}CO{sub 3}, KOH and tert-butyl amine, and the effect of the IEPs on the dye loading behavior of Zn{sub 2}SnO{sub 4} based photoelectrodes in dye sensitized solar cells (DSSCs). To produce highly crystalline, uniform sized Zn{sub 2}SnO{sub 4} nanoparticles, hydrothermal processing parameters, such as reaction temperature, time, and the mineralizers used have been critically adjusted. The structural and morphological features of the as-synthesized Zn{sub 2}SnO{sub 4} nanoparticles have been observed using both scanning and transmission electron microscopy. For the surface state characterization of shape- and size-controlled Zn{sub 2}SnO{sub 4} nanoparticles, the IEPs of Zn{sub 2}SnO{sub 4} surfaces were determined through zeta potential measurements. The IEPs were found to be 5.7, 7.4 and 8.1 for Zn{sub 2}SnO{sub 4} nanoparticles formed using Na{sub 2}CO{sub 3}, KOH and tert-butyl amine, respectively, suggesting that the surface properties of Zn{sub 2}SnO{sub 4} nanoparticles can be manipulated through the choice of the mineralizers used during the hydrothermal reaction. The amount of N719 dye loading on the surfaces of Zn{sub 2}SnO{sub 4} electrodes having different IEPs was also evaluated. It was revealed that the higher the IEP, the higher the dye loading amount, which means that the IEP mainly affects the dye loading at the dye-metal oxide interface. - Highlights: {yields} The effect of various mineralizers on the isoelectric point of Zn{sub 2}SnO{sub 4} was discussed. {yields} The IEP of Zn{sub 2}SnO{sub 4} can be modified by the choice of mineralizer. {yields} Change in IEP affects the surface properties and the morphology of Zn{sub 2}SnO{sub 4} particles. {yields} Modified surface affects the N719 dye loading behaviour of the Zn{sub 2}SnO{sub 4} based DSSCs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Generation of electric-field stabilized zirconium monoxide secondary phase within cubic zirconia

Flash sintering of cubic yttria-stabilized zirconia has been studied via in situ energy dispersive diffraction. A secondary rocksalt-phase zirconium monoxide was observed emerging from the primary fluorite-phase zirconium dioxide, previously only observed as a thin interlayer at metal-oxide interfaces, upon application of a direct current electric field. The average secondary phase intensity rose over extended flow of direct current through the ceramic, faded upon removal of the field and disappeared entirely upon application of an alternating current electric field. The results indicate that the sustained application of a direct current electric field can result in significant electrochemical reduction of zirconia under high current density conditions. Poor sinterability and cracking under direct current is apparent and potential mechanisms discussed therein.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Interfacial Stabilization of Metastable TiO 2 Films

This work demonstrates a phenomenon that preserves the traditionally metastable anatase crystal structure of thin titania (TiO 2 ) films along a two-dimensional oxide interface at temperatures well in excess of those that normally trigger a full polymorphic transformation to rutile in higher dimensionality crystalline powders. Whereas atomic surface mobility appears to dominate polymorph transformation processes within bulk TiO 2 powders, a simple reduction in dimensionality to a two-dimensional TiO 2 film (ca. 50–200 nm thick), supported upon a substrate, leads to a remarkable resistance to the calcination-induced anatase-to-rutile transformation. This stabilization does not appear to be specifically reliant on substrate character given its persistence for TiO 2 films prepared on amorphous silica (SiO 2 ) as well as crystalline TiO 2 substrates. Instead, interface-mediated coordination of the TiO 2 film with the substrate, and the inherent confinement of crystallites in two dimensions, is believed to resist polymorph transformation by mitigation of the atomic surface mobility. Furthermore, only when temperatures (i.e., >800 °C) that are conducive to bulk atomic mobilization are reached does reconstructive grain growth convert the film into the thermodynamically stable rutile crystal structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Extended Oxygen Octahedral Tilt Proximity near Oxide Heterostructures

The oxide interfaces between materials with different structural symmetries have been actively studied due to their novel physical properties. However, the investigation of intriguing interfacial phenomena caused by the oxygen octahedral tilt (OOT) proximity effect has not been fully exploited, as there is still no clear understanding of what determines the proximity length and what the underlying control mechanism is. Here, we achieved scalability of the OOT proximity effect in SrRuO 3 (SRO) by epitaxial strain near the SRO/SrTiO 3 heterointerface. We demonstrated that the OOT proximity length scale of SRO is extended from 4 unit cells to 14 unit cells by employing advanced scanning transmission electron microscopy. We also suggest that this variation may originate from changes in phonon dispersions due to electron-phonon coupling in SRO. Here, this study will provide in-depth insights into the structural gradients of correlated systems and facilitate potential device applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorod support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.

Lin, Yuyuan↗
DOE OSTI2019

Mitigating Measurement Artifacts in TOF-SIMS Analysis of Perovskite Solar Cells

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is one of the few techniques that can specifically distinguish between organic cations such as methylammonium and formamidinium. Distinguishing between these two species can lead to specific insight into the origins and evolution of compositional inhomogeneity and chemical gradients in halide perovskite solar cells, which appears to be a key to advancing the technology. TOF-SIMS can obtain chemical information from hybrid organic-inorganic perovskite solar cells (PSCs) in up to three dimensions, while not simply splitting the organic components into their molecular constituents (C, H, and N for both methylammonium and formamidinium), unlike other characterization methods. Here, we report on the apparently ubiquitous A-site organic cation gradient measured when doing TOF-SIMS depth-profiling of PSC films. Using thermomechanical methods to cleave perovskite samples at the buried glass/transparent conducting oxide interface enables depth profiling in a reverse direction from normal depth profiling (backside depth profiling). When comparing the backside depth profiles to the traditional front side profiled devices, an identical slight gradient in the A-site organic cation signal is observed in each case. This indicates that the apparent A-site cation gradient is a measurement artifact due to beam damage from the primary ion beam causing a continually decreasing ion yield for secondary ions of methylammonium and formamidinium. This is due to subsurface implantation and bond breaking from the 30 keV bismuth primary ion beam impact when profiling with too high of a data density. Here, we show that the beam-generated artifact associated with this damage can mostly be mitigated by altering the measurement conditions. We also report on a new method of depth profiling applied to PSC films that enables enhanced sensitivity to halide ions in positive measurement polarity, which can eliminate the need for a second measurement in negative polarity in most cases.

14 SOLAR ENERGY↗
DOE OSTI2019

MoS 2 –OH Bilayer-Mediated Growth of Inch-Sized Monolayer MoS 2 on Arbitrary Substrates

Due to remarkable electronic property, optical transparency, and mechanical flexibility, monolayer molybdenum disulfide (MoS 2 ) has been demonstrated to be promising for electronic and optoelectronic devices. To date, the growth of high-quality and large-scale monolayer MoS 2 has been one of the main challenges for practical applications. In this paper, we present a MoS 2 –OH bilayer-mediated method that can fabricate inch-sized monolayer MoS 2 on arbitrary substrates. This approach relies on a layer of hydroxide groups (-OH) that are preferentially attached to the (001) surface of MoS 2 to form a MoS 2 –OH bilayer structure for growth of large-area monolayer MoS 2 during the growth process. Specifically, the hydroxide layer impedes vertical growth of MoS 2 layers along the [001] zone axis, promoting the monolayer growth of MoS 2 , constrains growth of the MoS 2 monolayer only in the lateral direction into larger area, and effectively reduces sulfur vacancies and defects according to density functional theory calculations. Finally, the hydroxide groups advantageously prevent the MoS 2 from interface oxidation in air, rendering high-quality MoS 2 monolayers with carrier mobility up to ~30 cm 2 V –1 s –1 . Using this approach, inch-sized uniform monolayer MoS 2 has been fabricated on the sapphire and mica and high-quality monolayer MoS 2 of single-crystalline domains exceeding 200 μm has been grown on various substrates including amorphous SiO 2 and quartz and crystalline Si, SiC, Si 3 N 4 , and graphene Finally, this method provides a new opportunity for the monolayer growth of other two-dimensional transition metal dichalcogenides such as WS 2 and MoSe 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2014

Correlating interfacial octahedral rotations with magnetism in (LaMnO3+δ)N/(SrTiO3)N superlattices

Lattice distortion due to oxygen octahedral rotations have a significant role in mediating the magnetism in oxides, and recently attracts a lot of interests in the study of complex oxides interface. However, the direct experimental evidence for the interrelation between octahedral rotation and magnetism at interface is scarce. Here we demonstrate that interfacial octahedral rotation are closely linked to the strongly modified ferromagnetism in (LaMnO3+delta)(N)/(SrTiO3)(N) superlattices. The maximized ferromagnetic moment in the N = 6 superlattice is accompanied by a metastable structure (space group Imcm) featuring minimal octahedral rotations (a(-) a(-) c(-), alpha similar to 4.2 degrees, gamma similar to 0.5 degrees). Quenched ferromagnetism for N<4 superlattices is correlated to a substantially enhanced c axis octahedral rotation (a(-) a(-) c(-), alpha similar to 3.8 degrees, gamma similar to 8 degrees for N = 2). Monte-Carlo simulation based on double-exchange model qualitatively reproduces the experimental observation, confirming the correlation between octahedral rotation and magnetism. Our study demonstrates that engineering superlattices with controllable interfacial structures can be a feasible new route in realizing functional magnetic materials.

Zhai, Xiaofang↗
DOE OSTI2015

Engineering two-dimensional superconductivity and Rashba spin–orbit coupling in LaAlO 3 /SrTiO 3 quantum wells by selective orbital occupancy

We find the discovery of two-dimensional electron gases (2DEGs) at oxide interfaces—involving electrons in narrow d-bands—has broken new ground, enabling the access to correlated states that are unreachable in conventional semiconductors based on s- and p- electrons. There is a growing consensus that emerging properties at these novel quantum wells—such as 2D superconductivity and magnetism—are intimately connected to specific orbital symmetries in the 2DEG sub-band structure. Here we show that crystal orientation allows selective orbital occupancy, disclosing unprecedented ways to tailor the 2DEG properties. By carrying out electrostatic gating experiments in LaAlO 3 /SrTiO 3 wells of different crystal orientations, we show that the spatial extension and anisotropy of the 2D superconductivity and the Rashba spin–orbit field can be largely modulated by controlling the 2DEG sub-band filling. Such an orientational tuning expands the possibilities for electronic engineering of 2DEGs at LaAI0 3 /SrTio 3 interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Carrier density and disorder tuned superconductor-metal transition in a two-dimensional electron system

Quantum ground states that arise at atomically controlled oxide interfaces provide an opportunity to address key questions in condensed matter physics, including the nature of two-dimensional metallic behaviour often observed adjacent to superconductivity. At the superconducting LaAlO 3 /SrTiO 3 interface, a metallic ground state emerges upon the collapse of superconductivity with field-effect gating and is accompanied with a pseudogap. Here we utilize independent control of carrier density and disorder of the interfacial superconductor using dual electrostatic gates, which enables the comprehensive examination of the electronic phase diagram approaching zero temperature. We find that the pseudogap corresponds to precursor pairing, and the onset of long-range phase coherence forms a two-dimensional superconducting dome as a function of the dual-gate voltages. In conclusion, the gate-tuned superconductor–metal transitions are driven by macroscopic phase fluctuations of Josephson coupled superconducting puddles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Heteroepitaxial vertical perovskite hot-electron transistors down to the monolayer limit

Two-dimensional heterostructures combined with vertical geometries are candidates to probe and utilize the physical properties of atomically-thin materials. The vertical configuration enables a unique form of hot-carrier spectroscopy as well as atomic-scale devices. Here, we present the room-temperature evolution of heteroepitaxial perovskite hot-electron transistors using a SrRuO 3 base down to the monolayer limit ( ~ 4 Å). As a fundamental electronic probe, we observe an abrupt transition in the hot-electron mean free path as a function of base thickness, coinciding with the thickness-dependent resistive transition. As a path towards devices, we demonstrate the integrated synthesis of perovskite one-dimensional electrical edge contacts using water-soluble and growth-compatible Sr 3 Al 2 O 6 hard masks. Edge-contacted monolayer-base transistors exhibit on/off ratios reaching ~ 10 8 , complete electrostatic screening by the base manifesting pure hot-electron injection, and excellent scaling of the output current density with device dimensions. These results open new avenues for incorporating emergent phenomena at oxide interfaces and in heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Thermal stability and coalescence dynamics of exsolved metal nanoparticles at charged perovskite surfaces

Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts’ functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment. Nanoparticles that exsolve at the surface of the acceptor-type fast-oxygen-ion-conductor SrTi 0.95 Ni 0.05 O 3–δ (STNi) show a high surface mobility leading to a very low thermal stability compared to nanoparticles that exsolve at the surface of donor-type SrTi 0.9 Nb 0.05 Ni 0.05 O 3–δ (STNNi). Our analysis indicates that the low thermal stability of exsolved nanoparticles at the acceptor-doped perovskite surface is linked to a high oxygen vacancy concentration at the nanoparticle-oxide interface. For catalysts that require fast oxygen exchange kinetics, exsolution synthesis routes in dry hydrogen conditions may hence lead to accelerated degradation, while humid reaction conditions may mitigate this failure mechanism.

25 ENERGY STORAGE↗
DOE OSTI2018

Collapse of superconductivity in cuprates via ultrafast quenching of phase coherence

The possibility of driving phase transitions in low-density condensates through the loss of phase coherence alone has far-reaching implications for the study of quantum phases of matter. This has inspired the development of tools to control and explore the collective properties of condensate phases via phase fluctuations. Electrically gated oxide interfaces, ultracold Fermi atoms and cuprate superconductors, which are characterized by an intrinsically small phase stiffness, are paradigmatic examples where these tools are having a dramatic impact. In this study, we use light pulses shorter than the internal thermalization time to drive and probe the phase fragility of the Bi 2 Sr 2 CaCu 2 O 8+δ cuprate superconductor, completely melting the superconducting condensate without affecting the pairing strength. The resulting ultrafast dynamics of phase fluctuations and charge excitations are captured and disentangled by time-resolved photoemission spectroscopy. This work demonstrates the dominant role of phase coherence in the superconductor-to-normal state phase transition and offers a benchmark for non-equilibrium spectroscopic investigations of the cuprate phase diagram.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗