Materials Science (cond-mat.mtrl-sci)

Abstract: The crystallographic orientation of 3D materials grown over 2D material-covered substrates is one of the critical factors in discerning the true growth mechanism among competing possibilities, including remote epitaxy, van der Waals epitaxy, and pinhole-seeded lateral epitaxy also known as thru-hole epitaxy. However, definitive identification demands meticulous investigation to accurately interpret experimentally observed crystallographic orientations, as misinterpretation can lead to mistaken conclusions regarding the underlying growth mechanism. In this study, we demonstrate that GaN domains exhibit orientation disparities when grown on both bare and partly graphene-covered $m$-plane sapphire substrates. Comprehensive measurements of crystallographic orientation unambiguously reveal that GaN domains adopt (100) and (103) orientations even when grown under identical growth conditions on bare and partly graphene-covered $m$-plane sapphire substrates, respectively. Particularly, high-resolution transmission electron microscopy unequivocally establishes that GaN grown over partly graphene-covered $m$-plane sapphire substrates started to nucleate on the exposed sapphire surface. Our research elucidates that crystallographic orientation disparities can arise even from thru-hole epitaxy, challenging the commonly accepted notion that such disparities cannot be attributed to thru-hole epitaxy when grown under identical growth conditions.

Abstract: Two-dimensional (2D) tin monoxide (SnO) has attracted much attention owing to its distinctive electronic and optical properties, which render itself suitable as a channel material in field effect transistors (FETs). However, upon contact with metals for such applications, the Fermi level pinning effect may occur, where states are induced in its band gap by the metal, hindering its intrinsic semiconducting properties. We propose the insertion of graphene at the contact interface to alleviate the metal-induced gap states. By using gold (Au) as the electrode material and monolayer SnO (mSnO) as the channel material, the geometry, bonding strength, charge transfer and tunnel barriers of charges, and electronic properties including the work function, band structure, density of states, and Schottky barriers are thoroughly investigated using first-principles calculations for the structures with and without graphene to reveal the contact behaviours and Fermi level depinning mechanism. It has been demonstrated that strong covalent bonding is formed between gold and mSnO, while the graphene interlayer forms weak van der Waals interaction with both materials, which minimises the perturbance to the band structure of mSnO. The effects of out-of-plane compression are also analysed to assess the performance of the contact under mechanical deformation, and a feasible fabrication route for the heterostructure with graphene is proposed. This work systematically explores the properties of the Au-mSnO contact for applications in FETs and provides thorough guidance for future exploitation of 2D materials in various electronic applications and for selection of buffer layers to improve metal-semiconductor contact.

Abstract: In the search for novel intermetallic ternary alloys, much of the effort goes into performing a large number of ab-initio calculations covering a wide range of compositions and structures. These are essential to build a reliable convex hull diagram. While density functional theory (DFT) provides accurate predictions for many systems, its computational overheads set a throughput limit on the number of hypothetical phases that can be probed. Here, we demonstrate how an ensemble of machine-learning spectral neighbor-analysis potentials (SNAPs) can be integrated into a workflow for the construction of accurate ternary convex hull diagrams, highlighting regions fertile for materials discovery. Our workflow relies on using available binary-alloy data both to train the SNAP models and to create prototypes for ternary phases. From the prototype structures, all unique ternary decorations are created and used to form a pool of candidate compounds. The SNAPs are then used to pre-relax the structures and screen the most favourable prototypes, before using DFT to build the final phase diagram. As constructed, the proposed workflow relies on no extra first-principles data to train the machine-learning surrogate model and yields a DFT-level accurate convex hull. We demonstrate its efficacy by investigating the Cu-Ag-Au and Mo-Ta-W ternary systems.

Abstract: Cathodic protection (CP) was introduced two centuries ago and since has found widespread application in protecting structures such as pipelines, offshore installations, and bridges from corrosion. Despite its extensive use, the fundamental working mechanism of CP remains debated, particularly for metals in porous media such as soil. Here, we offer resolution to the long-standing debate by employing in-situ and ex-situ characterisation techniques coupled with electrochemical measurements to characterise the spatio-temporal changes occurring at the steel-electrolyte interface. We show that upon CP, the interfacial electrolyte undergoes alkalinisation and deoxygenation, and that depending on polarisation conditions, an iron oxide film can simultaneously form on the steel surface. We further demonstrate that these changes in interfacial electrolyte chemistry and steel surface state result in altered anodic and cathodic reactions and their kinetics. We propose a mechanism of CP that integrates the long debated theories, based on both concentration and activation polarisation, complimentarily. Implications of this coherent scientific understanding for enhancing corrosion protection technologies and the safe, economic, and environmental-friendly operation of critical steel-based infrastructures are discussed.

Abstract: When H, the lightest, smallest and most abundant atom in the universe, makes its way into a high-strength alloy (>650 MPa), the material's load-bearing capacity is abruptly lost. This phenomenon, known as H embrittlement, was responsible for the catastrophic and unpredictable failure of large engineering structures in service. The inherent antagonism between high strength requirements and H embrittlement susceptibility strongly hinders the design of lightweight yet reliable structural components needed for carbon-free hydrogen-propelled industries and reduced-emission transportation solutions. Inexpensive and scalable alloying and microstructural solutions that enable both, an intrinsically high resilience to H and high mechanical performance, must be found. Here we introduce a counterintuitive strategy to exploit typically undesired chemical heterogeneity within the material's microstructure that allows the local enhancement of crack resistance and local H trapping, thereby enhancing the resistance against H embrittlement. We deploy this approach to a lightweight, high-strength steel and produce a high-number density Mn-rich zones dispersed within the microstructure. These solute-rich buffer regions allow for local micro-tuning of the phase stability, arresting H-induced microcracks thus interrupting the H-assisted damage evolution chain, regardless of how and when H is introduced and also regardless of the underlying embrittling mechanisms. A superior H embrittlement resistance, increased by a factor of two compared to a reference material with a homogeneous solute distribution within each microstructure constituent, is achieved at no expense of the material's strength and ductility.

Abstract: Graphyne (GY) and graphdiyne (GDY)-based materials represent an intriguing class of two-dimensional (2D) carbon-rich networks with tunable structures and properties surpassing those of graphene. However, the challenge of fabricating atomically well-defined crystalline GY/GDY-based systems largely hinders detailed electronic structure characterizations. Here, we report the emergence of an unconventional band structure in mesoscopically regular (~1 {\mu}m) metallated GDY sheets featuring a honeycomb lattice on Ag(111) substrates. Employing complementary scanning tunnelling and angle-resolved photoemission spectroscopies, electronic band formation with a gap of 2.5 eV is rigorously determined in agreement with real-space electronic characteristics. Extensive density functional theory calculations corroborate our observations as well as recent theoretical predictions that doubly degenerate frontier molecular orbitals on a honeycomb lattice give rise to flat, Dirac and Kagome bands close to Fermi level. These results illustrate the tremendous potential of engineering novel band structures via molecular orbital and lattice symmetries in atomically precise 2D carbon scaffolds.

Abstract: Piezoelectricity of organic polymers has attracted increasing interest because of several advantages they exhibit over traditional inorganic ceramics. While most organic piezoelectrics rely on the presence of intrinsic local dipoles, a highly nonlocal electronic polarization can be foreseen in conjugated polymers, characterised by delocalized and highly responsive ${\pi}$-electrons. These 1D systems represent a physical realization of a Thouless pump, a mechanism of adiabatic charge transport of topological nature which results, as shown in this work, in anomalously large dynamical effective charges, inversely proportional to the band gap energy. A structural (ferroelectric) phase transition further contributes to an enhancement of the piezoelectric response reminiscent of that observed in piezoelectric perovskites close to morphotropic phase boundaries. First-principles Density Functional Theory (DFT) calculations performed in two representative conjugated polymers using hybrid functionals, show that state-of-the-art organic piezoelectric are outperformed by piezoelectric conjugated polymers, mostly thanks to strongly anomalous effective charges of carbon, larger than 5e - ordinary values being of the order of 1e - and reaching the giant value of 30e for band gaps of the order of 1 eV.

Abstract: This study describes computer simulations of carbonization and graphite formation, including the effects of hydrogen, nitrogen, oxygen, and sulfur. We introduce a novel technique to simulate carbonization, "Simulation of Thermal Emission of Atoms and Molecules (STEAM)," designed to elucidate the removal of volatiles and density variations in carbonization residue. The investigation extensively analyzes the functional groups that endure through high-temperature carbonization and examines the graphitization processes in carbon-rich materials containing non-carbon "impurity elements". The physical, vibrational, and electronic attributes of impure amorphous graphite are analyzed, and the impact of nitrogen on electronic conduction is investigated, revealing its substitutional integration into the sp$^2$ layered network.

Abstract: Stress-driven segregation at dislocations can lead to structural transitions between different linear complexion states. In this work, we examine how platelet array linear complexions influence dislocation motion and quantify the associated strengthening effect in Al-Cu alloys using atomistic simulations. The presence of platelet complexions leads to faceting of the dislocations, with nanoscale segments climbing upwards along the platelet growth direction, resulting in a complex non-planar configuration that restricts subsequent dislocation motion. Upon deformation, the leading partial dislocation must climb down from the platelet complexions first, followed by a similar sequence at the trailing partial dislocation, in order to overcome the precipitates and commence plastic slip. The dislocation depinning mechanism of linear complexions is strikingly different from traditional precipitation-strengthened alloys, where dislocations overcome obstacles by either shearing through or looping around obstacles. The critical shear stress required to unpin dislocations from platelet complexions is found to be inversely proportional to precipitate spacing, which includes not just the open space (as observed in Orowan bowing) but also the region along the platelet particle where climb occurs. Thus, platelet linear complexions provide a new way to modify dislocation structure directly and improve the mechanical properties of metal alloys.

Abstract: Here we present the family of titanium-based kagome metals of the form LnTi$_3$Bi$_4$ (Ln: La...Gd$^{3+}$, Eu$^{2+}$, Yb$^{2+}$). Single crystal growth methods are presented alongside detailed magnetic and thermodynamic measurements. The orthorhombic (\textit{Fmmm}) LnTi$_3$Bi$_4$ family of compounds exhibit slightly distorted titanium-based kagome nets interwoven with zig-zag lanthanide-based (Ln) chains. Crystals are easily exfoliated parallel to the kagome sheets and angular resolved photoemission (ARPES) measurements highlight the intricacy of the electronic structure in these compounds, with Dirac points existing at the Fermi level. The magnetic properties and the associated anisotropy emerge from the quasi-1D zig-zag chains of Ln, and impart a wide array of magnetic ground states ranging from anisotropic ferromagnetism to complex antiferromagnetism with a cascade of metamagnetic transitions. Kagome metals continue to provide a rich direction for the exploration of magnetic, topologic, and highly correlated behavior. Our work here introduces the LnTi$_3$Bi$_4$ compounds to augment the continuously expanding suite of complex and interesting kagome materials.

Abstract: Dispersed impurities in diamond present a flourishing platform for research in quantum informatics, spintronics and single phonon emitters. Based on the vast pool of experimental and theoretical work describing impurity atoms in diamond, we review the configurations by the chemical element discussing the relevant atomic configurations and most important properties. Dopant structures expand from single to co-doping configurations, also combined with carbon vacancies. Despite of their importance, not much is known about the exact atomic configurations associated with the dopant structures beyond computational models, partially due to difficulties in their microscopic observation. To assess the visibility of these structures, we carry out image simulations to show that the heavier dopants may be easily discernible in scanning transmission electron microscopy annular dark field images, with a window of visibility of up to over $\pm$ 10 nm in defocus. We further present the first atomic resolution images of an impurity atom configuration (substitutional Er atom) in the diamond lattice, confirmed by a comparison to the simulated images. Overall, our results demonstrate that there is a vast research field waiting for the microscopy community in resolving the exact atomic structure of various impurity atom configurations in diamond.

Abstract: We present a generalization of AEMD approach, routinely applied to estimate thermal conductivity, to the more general case in which Soret and Dufour effects determine a coupled heat-mass transfer. We show that, by starting from microscopical definitions of heat and mass currents, conservation laws dictates the form of the differential equations governing the time evolution. In particular, we focus to the well specific case in which a closed-form solution of the system is possible and derive the analytical form of time-evolution of temperature and concentration scalar fields in the case in which step-like initial profiles are imposed across a rectangular simulation cell. The validity of this new generalized expression is finally validated using as benchamrk system a two-component Lennard-Jones liquid system, for which generalized diffusivities are estimated in different reduced temperature and density region of phase diagram.

Abstract: Segregation engineering has emerged as a promising pathway towards designing thermally stable nanocrystalline alloys with enhanced mechanical properties. However, the compositional and processing space for solute stabilized microstructures is vast, thus the application of high-throughput techniques to accelerate optimal material development is increasingly attractive. In this work, combinatorial synthesis is combined with high-throughput characterization techniques to explore microstructural transitions through annealing of a nanocrystalline ternary Al-base alloy containing a transition metal (TM=Ni) and rare earth dopant (RE=Y). A down-selected optimal composition with the highest thermal stability is annealed through in situ transmission electron microscopy, revealing that the removal of the RE species is correlated to a reduction in the microstructural stability at high temperatures as a result of variations in intermetallic phase formation. Results demonstrate the benefits of co-segregation for enhancing mechanical hardness and delaying the onset of microstructural instability.