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At least 919 records · Page 51
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DOE OSTI2025

Molecular Structure and Thermodynamics of CO 2 and Water Adsorption on Mica

The adsorption of CO 2 and water on clay surfaces plays a key role in applications, such as gas storage in saline aquifers and depleted hydrocarbon reservoirs, but is not yet fully understood. Here, we study the adsorption of CO 2 and water vapor using Grand Canonical Monte Carlo and molecular dynamics simulations. At a bulk pressure of 100 bar, pure CO 2 adsorbs strongly on mica and forms extensive layers next to it. CO 2 adsorption is lowered substantially if introducing water vapor above mica and is largely eliminated when the relative humidity (RH) approaches about 60%. When pure water vapor is introduced above a mica surface, a subnanometer thick liquid water film develops on it to form apparent liquid–solid and liquid–vapor interfaces simultaneously. Using the identification of truly interfacial molecules (ITIM) analysis, we delineate how individual water layers develop in this film as RH increases. We highlight that the water film is spatially heterogeneous and the true liquid–vapor interface emerges only at an RH of 60–80%. Introducing 100 bar of CO 2 into the water vapor above the mica surface modulates water adsorption nonlinearly: at RH = 0.01%, the water adsorption is reduced by ∼30%; as RH increases, the reduction is weakened, and eventually, enhancement of water adsorption by about 7% occurs at RH = 90%. These variations are attributed to the interplay of film thinning by high-pressure CO 2 , competition of mica surface sites by CO 2 molecules, and energetic and entropic stabilization of interfacial water by CO 2 molecules.

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

Revealing the Dynamics and Roles of Iron Incorporation in Nickel Hydroxide Water Oxidation Catalysts

We report the surface of an electrocatalyst undergoes dynamic chemical and structural transformations under electro-chemical operating conditions. There is a dynamic exchange of metal cations between the electrocatalyst and electrolyte. Understanding how iron in the electrolyte gets incorporated in the nickel hydroxide electrocatalyst is critical for pinpointing the roles of Fe during water oxidation. Here, we report that iron incorporation and oxygen evolution reaction (OER) are highly coupled, especially at high working potentials. The iron incorporation rate is much higher at OER potentials than that at the OER dormant state (low potentials). At OER potentials, iron incorporation favors electrochemically more reactive edge sites, as visualized by synchrotron X-ray fluorescence microscopy. Using X-ray absorption spectroscopy and density functional theory calculations, we show that Fe incorporation can suppress the oxidation of Ni and enhance the Ni reducibility, leading to improved OER catalytic activity. Our findings provide a holistic approach to understanding and tailoring Fe incorporation dynamics across the electrocatalyst-electrolyte interface, thus controlling catalytic processes.

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

Molecular dynamics study on the interfacial properties of mixtures of monomers of polyvinylpyrrolidone (PVP)-based battery binders on graphene and graphite surfaces

This study investigates the behavior of two different mixtures of monomers of polyvinylpyrrolidone (PVP)-based battery binders, polyvinylpyrrolidone:polyvinylidene difluoride (PVP:PVDF) and polyvinylpyrrolidone:polyacrylic acid (PVP:PAA), at graphene and graphite interfaces using classical molecular dynamics simulations. The aim is to identify the best performing monomer binder blend and carbon-based material for the design of battery-optimized energy devices. The PVP:PAA monomer binder blend and graphite are found to have the best interaction energies, densification upon adsorption, and more ordered structure. The adsorption of both monomer binder blends is strongly guided by the higher affinity of PVP and PAA monomeric molecules for the surfaces compared to PVDF. The structure of adsorbed layers of PVP:PVDF monomer binder blend on graphene and graphite develops more quickly than PVP:PAA, indicating faster kinetics. This study complements a previous density functional theory study recently reported by our group and contributes to a better understanding of the nanoscopic features of relevant interfacial regions involving mixtures of monomers of PVP-based battery binders and different carbon-based materials. In conclusion, the effect of a blend of commonly used monomer binders on carbon-based materials is essential for obtaining tightly bound anode and cathode active materials in lithium-ion batteries, which is crucial for designing battery-optimized energy devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Probing the Li 4 Ti 5 O 12 Interface Upon Lithium Uptake by Operando Small Angle Neutron Scattering

The formation of a solid–electrolyte interphase (SEI) on the surface of Li 4 Ti 5 O 12 (LTO) has become a highly controversial topic, with arguments for it and against it. However, prior studies supporting the formation of an SEI layer have typically suggested that a layer forms upon cycling of a cell, although the layer is probed after disassembling. In this study, cubic mesostructured LTO is synthesized with crystallite domain sizes between 3 and 4 nm and uniform pores with diameters ≤8 nm. The mean pore size is controlled between 4–8 nm through the use of a triblock amphipathic copolymer with a tunable hydrophobic block as template and by thermal treatment. The LTO morphology obtained is spherical and evolves upon heat treatment. We report these materials show excellent electrochemical performance, including high rate capability and capacity retention. The LTO material is subjected to operando small-angle neutron scattering and X-ray photoelectron spectroscopy experiments, which reveal that the highly debated SEI forms at potentials as high as 2.2 V, first as a LiF-rich layer and subsequently by the growth of a carbonaceous layer. These SEI products form first on the smaller pores before forming on the mesopores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Deep Understanding of Strong Metal Interface Confinement: A Journey of Pd/FeO x Catalysts

Tuning the atomic interface configuration of noble metals (NMs) and transition-metal oxides is an effective straightforward yet challenging strategy to modulate the activity and stability of heterogeneous catalysts. Herein, Pd supported on mesoporous Fe 2 O 3 with a high specific surface area was rationally designed and chosen to construct the Pd/iron oxide interface. As a versatile model, the physicochemical environments of Pd nanoparticles (NPs) could be precisely controlled by taming the reduction temperature. The experimental and density functional theory calculation results unveiled that the catalyst in the support–metal interface confinement (SMIC) state showed significantly enhanced catalytic activity and sintering resistance for CO oxidation. The constructed Fe sites at the interfaces between FeO x overlayers and Pd NPs not only provided additional coordinative unsaturated ferrous sites for the adsorption and activation of O 2 , thereby facilitating the activation efficiency of O 2 , but also impressively changed the reaction pathway of CO oxidation. As a result, the catalyst followed the Pd/Fe dual-site mechanism instead of the classical Mars–van Krevelen mechanism. For the catalyst in the strong metal–support interaction (SMSI) state, its catalytic activity was seriously suppressed because of the excessive encapsulation of the active Pd sites by FeO x overlayers. Thus, the present study therefore provides detailed insights into the SMIC and SMSI in ferric oxide-supported Pd catalysts, which could guide the preparation of highly efficient supported catalysts for practical applications.

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

Understanding the Impacts of Support–Polymer Interactions on the Dynamics of Poly(ethyleneimine) Confined in Mesoporous SBA-15

Supported amines are a promising class of CO 2 sorbents offering large uptake capacities and fast uptake rates. Additionally, among supported amines, poly(ethyleneimine) (PEI) physically impregnated in the mesopores of SBA-15 silica is widely used. Within these composite materials, the chain dynamics and morphologies of PEI strongly influence the CO 2 capture performance, yet little is known about chain and macromolecule mobility in confined pores. Here, we probe the impact of the support–PEI interactions on the dynamics and structures of PEI at the support interface and the corresponding impact on CO 2 uptake performance, which yields critical structure–property relationships. The pore walls of the support are grafted with organosilanes with different chemical end groups to differentiate interaction modes (spanning from strong attraction to repulsion) between the pore surface and PEI. Combinations of techniques, such as quasi-elastic neutron scattering (QENS), 1 H T 1 –T 2 relaxation correlation solid-state NMR, and molecular dynamics (MD) simulations, are used to comprehensively assess the physical properties of confined PEI. We hypothesized that PEI would have faster dynamics when subjected to less attractive or repulsive interactions. However, we discover that complex interfacial interactions resulted in complex structure–property relationships. Indeed, both the chain conformation of the surface-grafted chains and of the PEI around the surface influenced the chain mobility and CO 2 uptake performance. By coupling knowledge of the dynamics and distributions of PEI with CO 2 sorption performance and other characteristics, we determine that the macroscopic structures of the hybrid materials dictate the first rapid CO 2 uptake, and the rate of CO 2 sorption during the subsequent gradual uptake stage is determined by PEI chain motions that promote diffusive jumps of CO 2 through PEI-packed domains.

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

Developing a Chemical and Structural Understanding of the Surface Oxide in a Niobium Superconducting Qubit

We report superconducting thin films of niobium have been extensively employed in transmon qubit architectures. Although these architectures have demonstrated remarkable improvements in recent years, further improvements in performance through materials engineering will aid in large-scale deployment. Here, we use information retrieved from secondary ion mass spectrometry and electron microscopy to conduct a detailed assessment of the surface oxide that forms in ambient conditions for transmon test qubit devices patterned from a niobium film. We observe that this oxide exhibits a varying stoichiometry with NbO and NbO 2 found closer to the niobium film and Nb 2 O 5 found closer to the surface. In terms of structural analysis, we find that the Nb 2 O 5 region is semicrystalline in nature and exhibits randomly oriented grains on the order of 1-2 nm corresponding to monoclinic N-Nb 2 O 5 that are dispersed throughout an amorphous matrix. Using fluctuation electron microscopy, we are able to map the relative crystallinity in the Nb 2 O 5 region with nanometer spatial resolution. Through this correlative method, we observe that amorphous regions are more likely to contain oxygen vacancies and exhibit weaker bonds between the niobium and oxygen atoms. Based on these findings, we expect that oxygen vacancies likely serve as a decoherence mechanism in quantum systems.

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

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

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

Pick-and-Place Transfer of Arbitrary-Metal Electrodes for van der Waals Device Fabrication

Van der Waals electrode integration is a promising strategy to create nearly perfect interfaces between metals and 2D materials, with advantages such as eliminating Fermi-level pinning and reducing contact resistance. However, the lack of a simple, generalizable pick-and-place transfer technology has greatly hampered the wide use of this technique. Here, we demonstrate the pick-and-place transfer of prefabricated electrodes from reusable polished hydrogenated diamond substrates without the use of any sacrificial layers due to the inherent low-energy and dangling-bond-free nature of the hydrogenated diamond surface. The technique enables transfer of arbitrary-metal electrodes and an electrode array, as demonstrated by successful transfer of eight different elemental metals with work functions ranging from 4.22 to 5.65 eV. We also demonstrate the electrode array transfer for large-scale device fabrication. The mechanical transfer of metal electrodes from diamond to van der Waals materials creates atomically smooth interfaces with no interstitial impurities or disorder, as observed with cross-section high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. As a demonstration of its device application, we use the diamond transfer technique to create metal contacts to monolayer transition metal dichalcogenide semiconductors with high-work-function Pd, low-work-function Ti, and semimetal Bi to create n- and p-type field-effect transistors with low Schottky barrier heights. We also extend this technology to air-sensitive materials (trilayer 1T’ WTe 2 ) and other applications such as ambipolar transistors, Schottky diodes, and optoelectronics. This highly reliable and reproducible technology paves the way for new device architectures and high-performance devices.

2D materials↗
DOE OSTI2020

Correlation between the temperature evolution of the interfacial region and the growing dynamic cooperativity length scale

Here, we study experimentally the temperature evolution of the thickness of the interfacial layer, L int (T), between bulk matrices and the surface of nanoparticles in nanocomposites through broadband dielectric spectroscopy. Analyses revealed a power-law dependence between the logarithm of structural relaxation time in the interfacial layer, τ int (T), and the L int (T): ln τ i n t ( T ) / τ 0 ∝ L i n t β ( T ) / T , with τ 0 ~ 10 –12 s, and β index ~0.67 at high temperatures and ~1.7 at temperatures close to the glass transition temperature. In addition, our analysis revealed that the L int (T) is comparable to the length scale of dynamic heterogeneity estimated from previous nonlinear dielectric measurements and the four-point NMR [ξ NMR (T)], with L int (T) ~ ξ NMR (T). These observations may suggest a direct correlation between the L int (T) and the size of the cooperatively rearranging regions and have strong implications for understanding the dynamic heterogeneity and cooperativity in supercool liquids and their role in interfacial dynamics.

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

Composition‐Conditioning Agent for Doped Spiro‐OMeTAD to Realize Highly Efficient and Stable Perovskite Solar Cells

Abstract The doped Spiro‐OMeTAD hole transport layer (HTL) formed using the lithium bis(trifluoromethane) sulfonimide salt and 4‐tert‐butylpyridine with phenethylammonium iodide surface treatment on a perovskite film has continuously dominated the record power conversion efficiencies (PCEs) of perovskite solar cells (pero‐SCs). However, unstable HTL compositions and iodide salts can cause severe device degradation. In this study, an HTL composition‐conditioning agent (CCA), Spiro‐BD‐2OEG, is designed, which contains a Spiro‐OMeTAD‐like backbone, functional pyridine units, and oligo (ethylene glycol) chains. This finely designed CCA presents good miscibility with Spiro‐OMeTAD and its dopants and acts as a conditioning agent through weak bond interactions. As a result, the CCA‐regulated HTL shows a pinhole‐free and smooth morphology with enhanced Spiro‐OMeTAD ordering and improves dopant stability. In addition, the gradient‐distributed CCA in the HTL can narrow the energy level offset with the valence band of the perovskite. The resultant pero‐SCs exhibit an excellent PCE of 24.19% without any interface treatment and weak size dependence. A remarkable PCE of 22.63% is obtained even for a 1.004‐cm 2 device. Importantly, the strategy shows good universality and significantly promotes the long‐term stability of the pero‐SCs based on the classical doped Spiro‐OMeTAD.

Chemistry↗
DOE OSTI2023

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Evolution of Metastable Structures at Bimetallic Surfaces from Microscopy and Machine-Learning Molecular Dynamics

The restructuring of interfaces plays a crucial role in materials science and heterogeneous catalysis. Bimetallic systems, in particular, often adopt very different compositions and morphologies at surfaces compared to the bulk. For the first time, we reveal a detailed atomistic picture of long-time scale restructuring of Pd deposited on Ag using microscopy, spectroscopy, and novel simulation methods. By developing and performing accelerated machine-learning molecular dynamics followed by an automated analysis method, we discover and characterize previously unidentified surface restructuring mechanisms in an unbiased fashion, including Pd-Ag place exchange and Ag pop-out as well as step ascent and descent. Remarkably, layer-by-layer dissolution of Pd into Ag is always preceded by an encapsulation of Pd islands by Ag, resulting in a significant migration of Ag out of the surface and a formation of extensive vacancy pits within a period of microseconds. These metastable structures are of vital catalytic importance, as Ag-encapsulated Pd remains much more accessible to reactants than bulk-dissolved Pd. We report our approach is broadly applicable to complex multimetallic systems and enables the previously intractable mechanistic investigation of restructuring dynamics at atomic resolution.

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

Emergent Behavior at the Calcite–Water Interface during Reactive Transport in a Simple Microfluidic Channel

Geochemical reactive transport processes in natural mineral-fluid systems may produce a wide array of emergent phenomena that are difficult to predict from basic principles and to reproduce in model systems. In this study, we present experimental results obtained from a simple microfluidic system with which we explored the consequences of reacting the calcite (104) cleavage surface with an acidic Pb-bearing solution (pH = 3.5, [Pb] total = 5 mM) as a function of flow rate. This system is relevant to passive remediation systems for Pb-rich acid mine drainage. We observed periodic banding in the amounts of Pb sorption at flow velocities ≥ 926 μm s -1 , where the band spacing was spatially correlated with the amount of calcite dissolution and the development of micropyramidal topography on the calcite (104) surface. The equivalent coverage of Pb deposited in these Pb-rich bands was at least several monolayers per unit cell, yet there was no evidence for precipitation of any secondary Pb phase implying incorporation of Pb within the near-surface calcite lattice. We also observed spatial variations in nucleation and growth of euhedral secondary Pb-carbonate minerals hydrocerusite and cerussite at flow rates ≤ 278 μm s -1 ,. These findings demonstrate potential for exploiting the rich phenomenology afforded by the interplay among transport phenomena and chemical kinetics in experimental systems designed to yield deeper insights into geochemical self-organization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Controlling Metal–Organic Framework/ZnO Heterostructure Kinetics through Selective Ligand Binding to ZnO Surface Steps

Metal–organic framework (MOF) heterostructures exhibit unique properties beyond those of individual components, but their design requires an understanding of energetic and kinetic controls at MOF–substrate interfaces. Although the structural relationship has been widely used in heterostructure design, it overlooks the interplay between the organic ligand and the substrate which controls the kinetics and energetics of growth of the final structure. In this study, we used zeolitic imidazolate frameworks (ZIF-8) on ZnO as a model system to evaluate this interplay via in situ monitoring and simulations. Our results demonstrate multiple roles of the 2-methyl-imidazole (2-MIM) ligand as “dissolution-promoter”, “step-pinner”, and “terrace-binder” on the ZnO (001) face and “dissolution-promoter” and “terrace-binder” on the ZnO (100) face. Through these multiple face-specific roles, 2-MIM modulates ZnO dissolution kinetics and, hence, the Zn 2+ release rate, tuning local supersaturations that dictating the characteristic ZIF-8 crystallization kinetics on different substrate faces. The critical thickness for transition from 2D to 3D growth is dictated by competition between interfacial and strain energies. The atomic-scale mechanism of the coupled substrate dissolution and MOF growth, mediated by selective linker–substrate binding, furnishes a new synthesis pathway for other complex heterostructures.

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

Combined, time-resolved, in situ neutron reflectometry and X-ray diffraction analysis of dynamic SEI formation during electrochemical N 2 reduction

One means of improving performance for electrochemical ammonia production through the Li-mediated N 2 reduction reaction (Li-NRR) is by cycling the current driving the reaction between open-circuit conditions and periods of applied current density. Herein, we have investigated the dynamics of the electrode–electrolyte interface under Li-NRR conditions during current cycling using in situ time-resolved neutron reflectometry and grazing-incidence synchrotron X-ray diffraction. During cycling, measured neutron reflectivity curves indicated bilayer formation in which Li-containing species such as LiOH, Li 2 O, and small quantities of Li 3 N and metallic Li primarily appeared in a thin layer at the cathode surface, above which formed a much larger, porous, ‘solid–electrolyte interface’ (SEI) layer. Upon return to open-circuit conditions, Li-containing species quickly moved out of the thin layer, leaving a compact, stable layer of decomposition products underneath the SEI layer. This SEI layer concomitantly filled with electrolyte or dissolved, becoming indistinguishable from the electrolyte via contrast in scattering-length density (SLD). During the second current cycle, Li-containing species again preferentially deposited directly atop the cathode, with the thick SEI-like layer again appearing within a minute. This SEI layer exhibited a lower SLD more quickly than in the first cycle, which might suggest that Li-containing species become distributed within the porous SEI layer. Furthermore, these time-resolved observations of SEI and plated layers during current cycling suggest that benefits associated with return to open-circuit conditions between periods of applied current density may be related to the concomitant loss of Li-containing species from a thin layer at the cathode surface into a porous SEI layer that becomes filled with electrolyte or dissolves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Accuracy in Resolving the First Hydration Layer on a Transition-Metal Oxide Surface: Experiment (AP-XPS) and Theory

Understanding the equilibrium conditions at the metal oxide/aqueous interface is a key component toward visualizing the structure of water in confined environments and differentiating the catalytic activity of transition-metal oxides. While ambient pressure X-ray photoelectron spectroscopy (AP-XPS) has been the primary technique to investigate the formation of a hydration layer on many surfaces, results over the extended relative humidity (RH) range accessible experimentally have not been compared quantitatively to theoretical predictions. With the use of first-principles theoretical methods and accumulated knowledge of AP-XPS spectral analysis, we do so here for a model surface, TiO 2 -terminated undoped SrTiO 3 (100) (STO). The measured distribution of OH and H 2 O coverages from vacuum up to the first hydration layer is in good agreement with a static density functional theory (DFT) configuration involving partial dissociation of H 2 O per Ti-atom mediated by H-bonding. Furthermore, ab initio molecular dynamics (AIMD) simulations at 300 K for select coverages (1/4, 1/2, and 1 ML) test the role of fluctuations and entropy in the competition between adsorption and dissociation with coverage. This comparison between theory and experiment for OH and H 2 O coverages on STO provides a foundation for a more quantitative assessment of the first hydration layer and associated competition between adsorption, dissociation, and H-bonding on transition-metal oxide surfaces.

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

Phonon confinement and interface lattice dynamics of ultrathin high- k rare earth sesquioxide films: the case of Eu 2 O 3 on YSZ(001)

The spatial confinement of atoms at surfaces and interfaces significantly alters the lattice dynamics of thin films, heterostructures and multilayers. Ultrathin films with high dielectric constants (high-k) are of paramount interest for applications as gate layers in current and future integrated circuits. Here we report a lattice dynamics study of high-k Eu 2 O 3 films with thicknesses of 21.3, 2.2, 1.3, and 0.8 nm deposited on YSZ(001). The Eu-partial phonon density of states (PDOS), obtained from nuclear inelastic scattering, exhibits broadening of the phonon peaks accompanied by up to a four-fold enhancement of the number of low-energy states compared to the ab initio calculated PDOS of a perfect Eu 2 O 3 crystal. Our analysis demonstrates that while the former effect reflects the reduced phonon lifetimes observed in thin films due to scattering from lattice defects, the latter phenomenon arises from an ultrathin EuO layer formed between the thin Eu 2 O 3 film and the YSZ(001) substrate. Thus, our work uncovers another potential source of vibrational anomalies in thin films and multilayers, which has to be cautiously considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗