Bulletin of the American Physical Society
APS March Meeting 2022
Volume 67, Number 3
Monday–Friday, March 14–18, 2022; Chicago
Session F66: Towards Application: Organics and SurfacesRecordings Available
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Chair: Andreas Riemann, Western Washington University Room: Hyatt Regency Hotel -Grant Park D |
Tuesday, March 15, 2022 8:00AM - 8:12AM |
F66.00001: Angstom-resolved Interfacial Structure in Organic-Inorganic Junctions Craig Schwartz Charge transport processes at interfaces play a crucial role in many processes. Here, the first soft x-ray second harmonic generation (SXR SHG) interfacial spectrum of a buried interface (boron–Parylene N) is reported. SXR SHG shows distinct spectral features that are not observed in x-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity. Comparison to electronic structure calculations indicates a boron-organic separation distance of 1.9 Å, with changes of less than 1 Å resulting in easily detectable SXR SHG spectral shifts (ca. hundreds of milli-electron volts). |
Tuesday, March 15, 2022 8:12AM - 8:24AM |
F66.00002: Heterotriangulene-based covalent networks on noble metal surfaces studied through STM and TOF-SIMS Harshavardhan Murali, Zachery Enderson, Raghunath Dasari, Timothy C Parker, Seth R Marder, Hong Li, Qingqing Dai, Jean-Luc E Bredas, Phillip N First
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Tuesday, March 15, 2022 8:24AM - 8:36AM |
F66.00003: Kinetically inhibiting lying-standing transitions to control growth of TCNE on Cu(111) Anna Werkovits, Andreas Jeindl, Lukas Hörmann, Johannes J Cartus, Oliver T Hofmann Interface polymorphs strongly govern the functionality of organic semiconductors. Especially when planar molecules adsorb in different orientations relative to the surface, properties significantly vary. To utilize this asset for tailoring interfaces often metastable structures must be stabilized, which might not be put into practice straightforwardly. |
Tuesday, March 15, 2022 8:36AM - 8:48AM |
F66.00004: Modeling Intercalated Graphene/O/Ir(111) for Organic Molecular Thin Films Jari Järvi, Milica Todorović, Patrick Rinke Organic charge transfer complexes (CTCs) are commonly grown on decoupled intercalated graphene (Gr) to avoid interference of the metallic substrate on their electronic properties. CTCs can feature different structural phases [1], but simulations are needed to resolve film morphologies. The complex substrate and large configurational space makes global ab-initio structure search intractable. In this study, we approximate the intercalated substrate using freestanding Gr with modified electronic structure. We confirm our Gr model with molecular adsorbates, which we identify with Bayesian optimization structure search (BOSS) [2] and density-functional theory (DFT). |
Tuesday, March 15, 2022 8:48AM - 9:00AM |
F66.00005: Kinetics of selecting polymorphism in organic molecular film growth Abdullah Al-Mahboob, Jerzy T Sadowski, Hem Raj Sharma, Julian Ledieu, Vincent Fournee, Percy Zahl, Elio Vescovo, Ronan McGrath The kinetics of nucleation and growth of metal-phthalocyanine thin films on Ag(100) surface were studied as a model system to elucidate the mechanism of polymorphic selectivity in organic molecular films. Real-time low-energy electron microscopy combined with scanning tunneling microscopy and DFT calculations revealed that the intermolecular vibrational modes determining kinematic discrete paths are specific to a particular in-plane arrangement of molecules, which in turns, tunes the growth and decay of polymorphic embryos. Phonon-constrained kinematic paths for interface-mediated kinetic processes, therefore, determine the phase transition and polymorph selection, rather than classical kinetic equilibrium. This phonon-constrained kinetics allows for selecting the growth mode and phase transition spontaneously from among competitive polymorphs. |
Tuesday, March 15, 2022 9:00AM - 9:12AM |
F66.00006: Materials genes of heterogeneous catalysis from clean experiments and artificial intelligence Lucas Foppa, Luca M Ghiringhelli, Frank Girgsdies, Maike Hashagen, Pierre Kube, Michael Hävecker, Spencer J. Carey, Andrey Tarasov, Peter Kraus, Frank Rosowski, Robert Schlögl, Annette Trunschke, Matthias Scheffler Heterogeneous catalysis is an example of a complex materials function governed by an intricate interplay of several processes. While modeling the full catalytic progression via first-principles statistical mechanics is impractical, we show how a tailored artificial-intelligence approach can be applied, even to a small number of materials, to determine the key descriptive parameters or materials genes reflecting the processes that trigger, facilitate, or hinder catalyst performance. We start from a consistent experimental set of clean data,[1] containing 12 selective-oxidation catalysts which were synthesized, fully characterized, and tested according to standardized protocols. Then, we apply the symbolic-regression SISSO approach[2] to identify the few most relevant materials properties that correlate, in a possibly nonlinear way, with the reactivity.[3] |
Tuesday, March 15, 2022 9:12AM - 9:24AM |
F66.00007: Multiscale modeling of a mechanochemical degradation path in aluminum surface coatings Jeremy A Scher, Tae Wook Heo, Stephen Weitzner, Yue Hao, Matthew P Kroonblawd Protective surface coatings inhibit aluminum corrosion pathways by replacing the highly reactive metal surface with one that is more chemically stable. Processes which erode these protective films render aluminum more susceptible to corrosion. We use ab initio molecular dynamics to model the erosion of γ-alumina surfaces and calculate associated reaction barriers while subjecting the oxide surface to environmental stressors, including vacuum, pooled water, and mechanical stress. We find that the presence of water reduces erosion reaction barriers by over 60% with respect to vacuum. Connections with microstructure-aware micromechanics models show that localized shear stresses can develop, which are predicted to couple with an aqueous environment resulting in further barrier reductions. These findings highlight the relevance of solvent and surface strain on aluminum corrosion and serve as a basis for predictive multiscale lifetime models. |
Tuesday, March 15, 2022 9:24AM - 9:36AM |
F66.00008: Controlling interface polymorphism of TCNE/Cu(111) with external electric fields Johannes J Cartus, Oliver T Hofmann Inorganic/organic interfaces can exhibit a rich variety of polymorphs, sometimes with drastic consequences for the interface properties. An example of these interfaces is tetracyanoethylene (TCNE) on Cu(111), which has recently been shown to exhibit a coverage driven phase transition from polymorphs of flat lying to standing molecules. The transition results in a change in work function of more than 3 eV, which makes this example system particularly interesting for applications in organic electronics. |
Tuesday, March 15, 2022 9:36AM - 9:48AM |
F66.00009: Developing an Ab Initio-Kinetic Model for the Prediction of Corrosion Behavior Rachel Gorelik, Peter Crozier, Arunima K Singh With the US economy incurring $200 billion annual losses due to corrosion, there is still a significant need for effective a priori models which enable the prediction of materials’ corrosion resistance, particularly within the field of materials discovery. While most current predictive models use fully empirical parameters, there is a value in the development of kinetic models which utilize solely quantum-mechanics-derived inputs. Therefore, as a first step in this direction, we develop an ab initio-kinetic model by applying the Pilling-Bedworth Rule (PBR), a metric commonly used to predict the passivation protectiveness of a given material based on mechanical driving forces. By automating this methodology for all single-element, binary, and ternary materials currently in the Materials Project database, we propose that this model can serve as a preliminary, low-cost screening step which can be applied to a wide range of materials for predicting their electrochemical stability. We then extend our methodology for a smaller subset of materials by also considering more complex kinetic models which incorporate a chemical transport driving force, which can then enable the creation of higher-accuracy ab initio models for the prediction of corrosion behavior. |
Tuesday, March 15, 2022 9:48AM - 10:00AM |
F66.00010: Molecular Beam Epitaxy (MBE) Growth of Model Thin Films to Study Interfacial Interactions Bilash KC, Robert F Klie, Jack Farrell, D. Bruce Buchholz, Jinglong Guo, Guennadi Evmenenko To address the increasing demand for energy storage technology, model thin films battery cathode systems are highly desirable since they avoid the complexity associated with polycrystalline or nano-sized powders which make detailed study of surfaces and interfaces difficult. However, the behavior of thin films depends highly on defect concentration, grain boundaries, and surface terminations [1,2]. An ideal way to study the material and interface properties is by isolating a particular crystallographic orientation and investigate the orientation dependent performance. To study such behavior, we have developed model thin films systems of different orientations by using molecular beam epitaxy (MBE) to study the interfacial ion diffusion and structural defects, and characterized them using aberration corrected transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS), and energy dispersive x-ray spectroscopy (EDXS). These model thin film cathode framework will be used for monovalent Li+ ions as well as divalent Mg2+ ions intercalation to quantify the evolution of defect concentrations and surface structures. |
Tuesday, March 15, 2022 10:00AM - 10:12AM |
F66.00011: Band-Engineered LaFeO3-LaNiO3 Thin Film Interfaces for Electrocatalysis of Water Rajendra Paudel, Andricus Burton, Marcelo A Kuroda, Byron H Farnum, Ryan B Comes Perovskite oxide thin films have been studied extensively for applications in electrocatalysis of water. Particularly, LaFeO3 and LaNiO3 have shown tremendous potential as catalysts in the oxygen evolution reaction. However, their catalytic performance needs to be improved significantly for commercial applications to compete with precious metal catalysts. Through band engineering we can fine tune the electronic properties of the material that might lead to the efficient energy conversion. By choosing suitable materials, charge can be driven across the heterostructure interface, which often leads to enhanced catalytic performance. The band alignment at the interface is crucial for charge transfer. In this work, we investigated the band offset at the LaFeO3/LaNiO3 interface combining experimental techniques as well as first principles calculations. |
Tuesday, March 15, 2022 10:12AM - 10:24AM |
F66.00012: Dynamic Gate Control of Aryldiazonium Chemistry on Graphene Field-Effect Transistors Anouk Béraud, Claudia M Bazan, Amira Bencherif, Delphine Bouilly Graphene field-effect transistors (GFETs) are promising candidates for sensor applications, but controlled functionalization of their surface is critical to ensure specific interactions with the chosen analyte. Among functionalization strategies, covalent adducts are most likely to ensure bond stability during multiple flow cycles. We demonstrate a state-of-the-art method using the gate electrode to precisely modulate and monitor aryldiazonium functionalization on parallel graphene devices. We first show that spontaneous functionalization of GFETs is heterogeneous with a low overall yield using characterization techniques such as on-device electrical measurements and Raman spectroscopy. We then propose to tune the gate voltage to dynamically enable or suppress the reaction and obtain a high homogeneity in our results. We also monitor, control, and analyze the functionalization kinetics in real-time. The mechanism for our approach is based on the Fermi level modulation of graphene, analogous to chemical, substrate-based, or electrochemical doping, but it has the practical advantage of being compatible with chip and device geometries. This work illustrates how we can utilize FET platforms to gain further insights on surface reactions on nanomaterials in real-time. |
Tuesday, March 15, 2022 10:24AM - 10:36AM |
F66.00013: 2-propanol Oxidation at Co3O4 (001)/H2O Interface: Insights from ab initio Molecular Dynamics Simulation Amir Hossein Omranpoor, Stephane Kenmoe, Eckhard Spohr The catalytic properties of the Co3O4 spinel for partial oxidation reactions have stimulated a great deal of interest in recent years. In order to gain more insight into the catalytic properties of the Co3O4 spinel, the oxidation of 2-propanol can serve as a model reaction. The reaction is simple enough to be studied in detail, yet sufficiently complex to provide selectivity for several possible reaction products. However, many such catalytic reactions take place not in the gas phase but rather in aqueous solution, for which knowledge in the literature is relatively limited. Therefore, we performed ab initio molecular dynamics simulations in order to study the oxidation of 2-propanol at the Co3O4(001)/H2O interface. In particular, we investigated the impact of surface termination, electrochemical environment, temperature and reactant concentration or coverage. Our investigation revealed the adsorption sites for both terminations of Co3O4(001) surface. In addition, it has been shown that there is competition between 2-propanol and H2O molecules for the adsorption sites. Furthermore, the B-termination has been found to be favourable for 2-propanol oxidation as a consequence of the formation of an ordered epitaxial water layer. |
Tuesday, March 15, 2022 10:36AM - 10:48AM |
F66.00014: Structure and corrosion resistance of ZrN-Ag coatings deposited by magnetron sputtering Claudia Patricia Mejia Villagran, Henry Samir Vanegas, Jhon Jairo Olaya Formation of nanostructured coatings of transition-metal nitride by introducing a small content of silver (Ag) has been a good strategy for enhancing physical properties of the materials for medical application. In this study, ZrN-Ag coatings with different Ag atomic contents are deposited by DC unbalanced reactive magnetron sputtering. The influence of the Ag atomic contents on the chemical composition, morphology and structure was characterized via energy-dispersive X-ray (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The XRD results showed that the addition of silver into a zirconium nitride generated a decrease in the crystallinity of the coatings, characterized by a decrease in intensity and a broadening of X-ray diffraction peaks. EDS results showed that coatings have 0%, 7% and 12% atomic in Ag contain. SEM results show us that the morphology changes from coliform to smoother structure with small silver dots, when silver content increases. The electrochemical behavior of the coatings in a ringer's lactate solution at 37 ° C was studied by electrochemical impedance spectroscopy (EIS). EIS results show that the better corrosion resistance is obtained for the coating with 7% atomic Ag and the corrosion resistance lower is ZrN to reference for day one and day nine. Finally, XPS results confirm that all coatings have oxide and oxynitrides in the surface of the coatings after the EIS test. |
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