Metallic Systems Research Articles

Epitaxial Fe/Rh bilayers for efficient spin-to-charge conversion

To address the spin pumping in the conventional ferromagnetic/“normal” metal systems, we fabricated 6 nm Fe/1–15 nm Rh epitaxial bilayers and determined the g-factor, magnetic anisotropy, and magnetization damping by combining both 0–40 GHz CPW-based frequency-dependent and cavity-based 9.56 GHz in-plane angular-dependent ferromagnetic resonance measurements at room temperature. Auger electron spectroscopy and low-energy electron diffraction show that Rh grows epitaxially on Fe. The epitaxial bilayers exhibit a high spin mixing conductance gmix↑↓=(2.9±0.2)×1019 m−2 and a spin diffusion length in Rhodium λsd=9.0±1.3 nm. This makes Rh comparable to Pt and Pd in terms of spin pumping and spin transport efficiency at room temperature.

Enthalpy-Driven Self-Healing in Thin Metallic Films on Flexible Substrates.

Self-healing microelectronics are needed for costly applications with limited or without access. They are needed in fields such as space exploration to increase lifetime and decrease both costs and the environmental impact. While advanced self-healing mechanisms for polymers are numerous, practical ways for self-healing in metal films have yet to be found. A concept for an autonomous intrinsic self-healing metallic film system is developed, allowing the healing of cracks in metallic films on flexible substrates. The concept relies on stabilizing metastable thin films with high mixing enthalpy via segregation barriers. This allows the films to possess autonomous intrinsic self-healing capabilities triggered by cracking at temperatures not detrimental to flexible microelectronics. The effect will be shown on metastable Mo1-xAgx thin films, stabilized via a Mo segregation barrier. Without a segregation barrier, the system is known to exhibit spontaneous Ag particle formation on the surface. This property is controlled and directed to heal cracks and partially restore the electro-mechanical properties of the multilayer system. This mechanism opens up the field of self-healing thin metallic films that could profoundly impact the design of future microelectronics.

A study on the thermomechanical response of various die attach metallic materials of power electronics

PurposeIn power electronics, there are various metallic material systems used as die attachments. The complete understanding of the thermomechanical behavior of such interconnections is very important. Therefore, this paper aims to examine the thermomechanical response of four famous die attach materials, including sintered silver, sintered nano-copper particles, gold-tin solders and silver-tin transient liquid phase (TLP) bonds, using nonlinear finite element analysis.Design/methodology/approachDuring the study, the mechanical properties of all die attach systems, including elastic and viscoplasticity parameters, are obtained from literature studies and hence incorporated into the numerical analysis. Subsequently, the bond stress–strain relationships, stored inelastic strain energies and equivalent plastic strains are thoroughly examined.FindingsThe results showed that the silver-tin TLP bonds are more likely to develop higher inelastic strain energy densities, while the sintered silver and copper interconnects would possess higher plastic strains and deformations. Suggesting higher damage to such metallic die attachments. The expensive gold-based solders have developed least inelastic strain energy densities and least plastic strains as well. Thus, they are expected to have improved fatigue performance compared to other bonding configurations.Originality/valueThis paper extensively investigates and compares the mechanical and thermal response of various metallic die attachments. In fact, there are no available research studies that discuss the behavior of such important die attachments of power electronics when exposed to mechanical and thermomechanical loads.

Research on the creep response of lead-free die attachments in power electronics

PurposeThe purpose of this paper is to investigate the thermomechanical response of four well-known lead-free die attach materials: sintered silver, sintered nano-copper particles, gold-tin solders and silver-tin transient liquid phase (TLP) bonds.Design/methodology/approachThis examination is conducted through finite element analysis. The mechanical properties of all die attach systems, including elastic and Anand creep parameters, are obtained from relevant literature and incorporated into the numerical analysis. Consequently, the bond stress-strain relationships, stored inelastic strain energies and equivalent plastic strains are thoroughly examined.FindingsThe results indicate that silver-tin TLP bonds are prone to exhibiting higher inelastic strain energy densities, while sintered silver and copper interconnects tend to possess higher levels of plastic strains and deformations. This suggests a higher susceptibility to damage in these metallic die attachments. On the other hand, the more expensive gold-based solders exhibit lower inelastic strain energy densities and plastic strains, implying an improved fatigue performance compared to other bonding configurations.Originality/valueThe utilization of different metallic material systems as die attachments in power electronics necessitates a comprehensive understanding of their thermomechanical behavior. Therefore, the results of the present paper can be useful in the die attach material selection in power electronics.

Loose bonding induced ultralow lattice thermal conductivity of a metallic crystal KNaRb

In the domain of metallic systems, electronic thermal conductivity typically governs heat transfer, while lattice (phononic) thermal conductivity (LTC) remains non-negligible magnitude. This study introduces the exceptional metallic material, cubic half-Heusler-type KNaRb, via phonon Boltzmann transport equation (BTE) resolution and first-principles calculations. KNaRb exhibits an ultralow LTC of 0.114 W/mK at room temperature, comparable to the lowest reported for metallic materials, contributing merely 0.66 % to overall thermal transport. Analysis attributes KNaRb's low LTC to low group velocity and strong anharmonicity, originating from its loosely bonded electronic structure. Acoustic modes, primarily from Rb atoms, dominate thermal transport. Examination of mean square displacement and potential energy profiles reveals significant movement of loosely bonded Rb atoms within KNaRb, acting as intrinsic "rattlers," inducing pronounced phonon anharmonicity and ultrashort lifetimes. This study advances understanding of heat conduction in metals, offering insights into materials with extremely low lattice thermal conductivity for potential future applications.

Spontaneous Liquefaction of Solid Metal-Liquid Metal Interfaces in Colloidal Binary Alloys.

Crystallization of alloys from a molten state is a fundamental process underpinning metallurgy. Here the direct imaging of an intermetallic precipitation reaction at equilibrium in a liquid-metal environment is demonstrated. It is shown that the outer layers of a solidified intermetallic are surprisingly unstable to the depths of several nanometers, fluctuating between a crystalline and a liquid state. This effect, referred to herein as crystal interface liquefaction, is observed at remarkably low temperatures and results in highly unstable crystal interfaces at temperatures exceeding 200 K below the bulk melting point of the solid. In general, any liquefaction process would occur at or close to the formal melting point of a solid, thus differentiating the observed liquefaction phenomenon from other processes such as surface pre-melting or conventional bulk melting. Crystal interface liquefaction is observed in a variety of binary alloy systems and as such, the findings may impact the understanding of crystallization and solidification processes in metallic systems and alloys more generally.

Mapping the Binary Covalent Alloy Space to Pursue Superior Nitrogen Reduction Reaction Catalysts

AbstractThe electrochemical nitrogen reduction reaction (NRR) has the potential to decarbonize industrial ammonia production. However, NRR has poor activity and selectivity versus the competing hydrogen evolution reaction for catalysts that adhere to scaling relations. Overcoming the limitations imposed by scaling relations requires more complex catalyst materials, however, evaluating materials beyond simple metal systems is a large combinatorial problem that requires an improved understanding of the electrocatalyst surface to rationally guide the discovery of superior catalysts. The study uses grand canonical density functional theory to uncover NRR trends on a large and disparate set of binary covalent alloys (BCA) with variable compositions and active‐site geometries. The studied BCAs generally follow scaling relations, albeit with larger variance and several systems that significantly break scaling. BCAs with early‐ to mid‐transition metals tend to lie near the volcano peak and activate the N2 triple bond via a side‐on binding configuration. Trends in the BCA space cannot be readily predicted using simple electronic descriptors, which is ascribed to the large geometric variability of the BCA surfaces. It is anticipated that these findings will provide a foundation for the rational design of superior NRR electrocatalysts with increasing material complexity.

Experimental study, simulation and technical–economic feasibility of an interesterification plant for hydrocarbons synthesis by using plastics and frying oil waste

This work presents the experimental assessment of a 20 mL batch reactor’s efficacy in converting plastic and oil residues into biofuels. The reactor, designed for ease of use, is heated using a metallic system. The experiments explore plastic solubilization at various temperatures and residence times, employing a mixture of distilled water and ethylene glycol as the solvent. Initial findings reveal that plastic solubilization requires a temperature of 350 °C with an ethylene glycol mole fraction of 0.35, whereas 250 °C suffices with a mole fraction of 0.58. Additionally, the study includes a process simulation of a plant utilizing a double fluidized bed gasifier and an economic evaluation of the interesterification/pyrolysis plant. Simulation results support project feasibility, estimating a total investment cost of approximately $12.99 million and annual operating expenses of around $17.98 million, with a projected payback period of about 5 years.

Conjugate heat transfer analysis of the transient thermal discharge of a metallic latent heat storage system

Thermal energy storage systems utilizing metallic phase change materials exhibit great potential as a technology for mobile applications, offering high storage densities and high thermal discharge rates. First experimental investigations show the functionality and performance characteristics of this system. For a deeper understanding of the thermal discharge, this paper presents a numerical model and analysis of the transient conjugate heat transfer. For validation of the numerical model, the results of the simulations are compared to the available experimental data. The investigated storage is based on an aluminum silicon alloy and a box-shaped graphite container design. In this system, heat extraction is achieved by forced convection of ambient air. The transient thermal discharge was simulated from 650 °C to 100 °C, and the solidification of the storage material at around 577 °C was simulated using an enthalpy-porosity approach. The discharge time and total heat flow show good agreement with the experimental data, indicating the model’s successful validation. An empirical study was carried out to determine the thermal contact resistance at the interface between the storage material and the graphite container. The present study contributes new physical insights regarding the thermal discharge of a novel metallic latent heat thermal energy storage system.

Frustration-induced quantum criticality in Ni-doped CePdAl as revealed by the µSR technique

In CePdAl, the 4f moments of cerium arrange to form a geometrically frustrated kagome lattice. Due to frustration, in addition to Kondo and Ruderman-Kittel-Kasuya-Yosida interactions, this metallic system shows a long-range magnetic order (LRO) with a TN of only 2.7 K. Upon Ni doping at the Pd sites, TN is further suppressed, to reach zero at a critical concentration xc≈0.15. Here, by using muon-spin relaxation and rotation (µSR), we investigate CePd1−xNixAl at a local level for five different Ni concentrations, both above and below xc. Like the parent CePdAl compound, for x=0.05, we observe an incommensurate LRO, which turns into a quasistatic magnetic order for x=0.1 and 0.14. More interestingly, away from xc, for x=0.16 and 0.18, we still observe a non-Fermi-liquid (NFL) regime, evidenced by a power-law divergence of the longitudinal relaxation at low temperatures. In this case, longitudinal field measurements exhibit a time-field scaling, indicative of cooperative spin dynamics that persists for x>xc. Furthermore, like the externally applied pressure, the chemical pressure induced by Ni doping suppresses the region below T*, characterized by a spin-liquid-like dynamical behavior. Our results suggest that the magnetic properties of CePdAl are similarly affected by the hydrostatic and the chemical pressure. We also confirm that the unusual NFL regime (compared with conventional quantum critical systems) is due to the presence of frustration that persists up to the highest Ni concentrations. Published by the American Physical Society 2024

Design, fabrication and validation of an electrical conductivity principle based two-phase detection sensor array for molten lead (Pb) based heavy metal coolants up to 600°C

Molten lead (Pb) and its alloys (PbBi and PbLi) are of immense interest for various nuclear engineering applications, including but not limited to advanced Lead-cooled Fast Reactors (LFRs), tritium Breeding Blankets (BBs) of fusion power plants and spallation targets for Accelerator-Driven Systems (ADS). Owing to their attractive thermophysical properties, these advanced fluids assert their candidacy to address the critical requirements of neutron multiplication, neutron moderation, high temperature coolants and tritium breeders, enabling the operation of next generation nuclear systems at high temperatures with better efficiencies. However, for numerous reasons such as a compromise of structural integrity at the heat transfer interface, presence of an inert cover gas during charging of molten metal in the loop, and the fusion fuel cycle itself may lead to molten metal-gas two-phase flows with high density ratios. At present, no effective diagnostics exist to detect such operational and accidental occurrences in high temperature molten metal systems resulting in a severe lack of relevant experimental studies. To address these limitations and to advance the current understanding toward two-phase regimes in high temperature Pb-based melts, the present work focuses on the design and assembly aspects of an electrical conductivity-based two-phase detection sensor array, utilizing high purity α-Al2O3 coatings with AlPO4 binder as electrical insulation layers. This paper discusses the design considerations, thermal analysis, systematic selection of structural/functional components along with preliminary results from the probe performance tests in very high temperature (600°C) static molten Pb column for real time detection of argon gas bubbles rising within the melt. Quantitative estimations of time-averaged void fraction, average bubble impaction frequency and average bubble residence time are presented from the preliminary experimental investigations.

Synthesis and characterization of ceramic high entropy carbide thin films from the Cr-Hf-Mo-Ta-W refractory metal system

We use reactive DC magnetron sputtering to showcase synthesis strategies for multicomponent carbides with the NaCl-type fcc structure and illustrate how deposition conditions allow controlling the formation of metallic and ceramic single phases in the Cr-Hf-Mo-Ta-W system. The synthesis is performed in argon flow and different acetylene flows from 0 to 12sccm, at ambient and elevated temperatures (700 °C), respectively, hindering/promoting the adatom diffusion. Structural and microstructural investigations reveal the formation of the bcc metallic phase (a=3.188−3.209Å) in films deposited without acetylene flow, also supported by ab initio density function theory (DFT) analysis of lattice parameters as a function of the C content. Experimentally, a bcc-to-fcc phase transition is observed through the formation of an amorphous coating. Contrarily, samples deposited in higher acetylene flow show an fcc multielement carbide phase (a=4.33−4.49 Å). The crystalline films reveal columnar morphology, while the amorphous ones are very dense. We report promising mechanical properties, with hardness up to 25±1GPa. The indentation moduli reach up to 319±6GPa and show trends consistent with DFT predictions. Our study paves the path towards the preparation of Cr-Hf-Mo-Ta-W multicomponent carbides by magnetron sputtering, showing promising microstructure as well as mechanical properties.

4f electron temperature driven ultrafast electron localization

Valence transitions in strongly correlated electron systems are caused by orbital hybridization and Coulomb interactions between localized and delocalized electrons. The transition can be triggered by changes in the electronic structure and is sensitive to temperature variations, applications of magnetic fields, and physical or chemical pressure. Launching the transition by photoelectric fields can directly excite the electronic states and thus provides an ideal platform to study the correlation among electrons on ultrafast timescales. The EuNi2(Si0.21Ge0.79)2 mixed-valence metal is an ideal material to investigate the valence transition of the Eu ions via the amplified orbital hybridization by the photoelectric field on subpicosecond timescales. A direct view on the 4f electron occupancy of the Eu ions is required to understand the microscopic origin of the transition. Here we probe the 4f electron states of EuNi2(Si0.21Ge0.79)2 at the sub-ps timescale after photoexcitation by x-ray absorption spectroscopy across the Eu M5-absorption edge. The observed spectral changes due to the excitation indicate a population change of total angular momentum multiplet states J = 0, 1, 2, and 3 of Eu3+ and the Eu2+ J = 7/2 multiplet state caused by an increase in 4f electron temperature that results in a 4f localization process. This electronic temperature increases combined with fluence-dependent screening accounts for the strongly nonlinear effective valence change. The data allow us to extract a time-dependent determination of an effective temperature of the 4f shell, which is also of great relevance in the understanding of metallic systems' properties, such as the ultrafast demagnetization of ferromagnetic rare-earth intermetallic and their all-optical magnetization switching. In addition, our results elucidate the energetics of charge fluctuations in valence-mixed electronic systems, which provide enriched knowledge regarding the role of valence transitions and orbital hybridization for quantum critical phenomena. Published by the American Physical Society 2024

Use of Unmanned Surface Vehicles (USVs) in Water Chemistry Studies.

Unmanned surface vehicles (USVs) equipped with integrated sensors are a tool valuable to several monitoring strategies, offering enhanced temporal and spatial coverage over specific timeframes, allowing for targeted examination of sites or events of interest. The elaboration of environmental monitoring programs has relied so far on periodic spot sampling at specific locations, followed by laboratory analysis, aiming at the evaluation of water quality at a catchment scale. For this purpose, automatic telemetric stations for specific parameters have been installed by the Institute of Marine Biological Resources and Inland Waters of Hellenic Centre for Marine Research (IMBRIW-HCMR) within several Greek rivers and lakes, providing continuous and temporal monitoring possibilities. In the present work, USVs were deployed by the Athens Water and Sewerage Company (EYDAP) as a cost-effective tool for the environmental monitoring of surface water bodies of interest, with emphasis on the spatial fluctuations of chlorophyll α, electrical conductivity, dissolved oxygen and pH, observed in Koumoundourou Lake and the rivers Acheloos, Asopos and Kifissos. The effectiveness of an innovative heavy metal (HM) system installed in the USV for the in situ measurements of copper and lead was also evaluated herewith. The results obtained demonstrate the advantages of USVs, setting the base for their application in real-time monitoring of chemical parameters including metals. Simultaneously, the requirements for accuracy and sensitivity improvement of HM sensors were noted, in order to permit full exploitation of USVs' capacities.

Interface engineering of hierarchical flower-like N, P, O-doped NixPy self-supported electrodes for highly efficient water-to-hydrogen fuel/oxygen conversion

Rational construction of efficient bifunctional catalysts with robust catalytic activity and durability is significant for overall water splitting (conversion between water and hydrogen fuel/oxygen) using non-precious metal systems. In this work, the hierarchically porous N, P, O-doped transition metal phosphate in the Ni foam (NF) electrode (hollow flower-like NPO/NixPy@NF) was prepared through facile hydrothermal method coupled with phosphorization treatment. The hierarchical hollow flower-like NPO/NixPy@NF electrodes exhibited high bifunctional activity and stability for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solutions. The optimized electrode showed low overpotentials of 76 and 240 mV for HER and OER to reach a current density of 10 mA cm−2, respectively. Notably, the NPO/NixPy@NF electrode only required a low voltage of 1.99 V to reach the current densities of 100 mA cm−2 with long-term stability for overall water splitting using the NPO/NixPy@NF|| NPO/NixPy@NF cell, surpassing that of the Pt/C-RuO2 (2.24 V@ 100 mA cm−2). The good catalytic and battery performance should be attributed to i) the open hierarchical structure that enhanced the mass transfer; ii) a highly conductive substrate that accelerated the electron transfer; iii) the rich heterojunction and strong synergy between Ni2P and Ni5P4 that improved the catalytic kinetic; iv) the proper-thickness amorphous phosphorus oxide nitride (PON) shell that realized the stability. This work demonstrates a promising methodology for designing bifunctional transition metal phosphides with high performance for efficient water splitting.

Non-destructive depth reconstruction of Al-Al2Cu layer structure with nanometer resolution using extreme ultraviolet coherence tomography

Non-destructive cross-sectional characterization of materials systems with a resolution in the nanometer range and the ability to allow for time-resolved in-situ studies is of great importance in material science. Here, we present such a measurements method, extreme ultraviolet coherence tomography (XCT). The method is non-destructive during sample preparation as well as during the measurement, which is distinguished by a negligible thermal load as compared to electron microscopy methods. Laser-generated radiation in the extreme ultraviolet (XUV) and soft x-ray range is used for characterization. The measurement principle is interferometric and the signal evaluation is performed via an iterative Fourier analysis. The method is demonstrated on the metallic material system Al-Al2Cu and compared to electron and atomic force microscopy measurements. We also present advanced reconstruction methods for XCT, which even allow for the determination of the roughness of outer and inner interfaces.

Recent advances in synchrotron X-ray studies of the atomic structures of metal alloys in liquid state

Research into the atomic structures of metal materials in the liquid state, their dynamic evolution versus temperature until the onset of crystal nucleation has been a central research topic in condensed matter physics and materials science for well over a century. However, research and basic understanding of the atomic structures of liquid metals are far less than those in the solid state of the same compositions. This review serves as a condensed collection of the most important research literature published so far in this field, providing a critical and focused review of the historical research development and progress in this field since the 1920s. In particular, the development of powerful synchrotron X-ray sources and the associated experimental techniques and sample environments for studying in-situ the atomic structures of different metallic systems. The key findings made in numerous pure metals and metallic alloy systems are critically reviewed and discussed with the focus on the results and new understandings of structural heterogeneities found inside a bulk liquid, at the liquid surface or liquid-solid interface. The possible future directions of research and development on the most advanced experimental and modeling techniques are envisaged and briefly discussed as well.

A correlated ferromagnetic polar metal by design.

Polar metals have recently garnered increasing interest because of their promising functionalities. Here we report the experimental realization of an intrinsic coexisting ferromagnetism, polar distortion and metallicity in quasi-two-dimensional Ca3Co3O8. This material crystallizes with alternating stacking of oxygen tetrahedral CoO4 monolayers and octahedral CoO6 bilayers. The ferromagnetic metallic state is confined within the quasi-two-dimensional CoO6 layers, and the broken inversion symmetry arises simultaneously from the Co displacements. The breaking of both spatial-inversion and time-reversal symmetries, along with their strong coupling, gives rise to an intrinsic magnetochiral anisotropy with exotic magnetic field-free non-reciprocal electrical resistivity. An extraordinarily robust topological Hall effect persists over a broad temperature-magnetic field phase space, arising from dipole-induced Rashba spin-orbit coupling. Our work not only provides a rich platform to explore the coupling between polarity and magnetism in a metallic system, with extensive potential applications, but also defines a novel design strategy to access exotic correlated electronic states.

Exploring Challenging Properties of Liquid Metallic Systems through Machine Learning: Liquid La and Li4Pb Systems.

In this machine learning (ML) study, we delved into the unique properties of liquid lanthanum and the Li4Pb alloy, revealing some unexpected features and also firmly establishing some of the debated characteristics. Leveraging interatomic potentials derived from ab initio calculations, our investigation achieved a level of precision comparable to first-principles methods while at the same time entering the hydrodynamic regime. We compared the structure factors and pair distribution functions to experimental data and unearthed distinctive collective excitations with intriguing features. Liquid lanthanum unveiled two transverse collective excitation branches, each closely tied to specific peaks in the velocity autocorrelation function spectrum. Furthermore, the analysis of the generalized specific heat ratio in the hydrodynamic regime investigated with the ML molecular dynamics simulations uncovered a peculiar behavior, impossible to discern with only ab initio simulations. Liquid Li4Pb, on the other hand, challenged existing claims by showcasing a rich array of branches in its longitudinal dispersion relation, including a high-frequency LiLi mode with a nonhydrodynamic optical character that maintains a finite value as q → 0. Additionally, we conducted an in-depth analysis of various transport coefficients, expanding our understanding of these liquid metallic systems. In summary, our ML approach yielded precise results, offering new and captivating insights into the structural and dynamic aspects of these materials.

Levitons in correlated nano-scale systems.

In this short review (written to celebrate David Campbell's 80th birthday), we provide a theoretical description of quantum transport in nanoscale systems in the presence of single-electron excitations generated by Lorentzian voltage drives, termed Levitons. These excitations allow us to realize the analog of quantum optics experiments using electrons instead of photons. Importantly, electrons in condensed matter systems are strongly affected by the presence of different types of non-trivial correlations, with no counterpart in the domain of photonic quantum optics. After providing a short introduction about Levitons in non-interacting systems, we focus on how they operate in the presence of two types of strong electronic correlations in nanoscale systems, such as those arising in the fractional quantum Hall effect or in superconducting systems. Specifically, we consider Levitons in a quantum Hall bar of the fractional quantum Hall effect, pinched by a quantum point contact, where anyons with fractional charge and statistics tunnel between opposite edges. In this case, a Leviton-Leviton interaction can be induced by the strongly correlated background. Concerning the effect of superconducting correlations on Levitons, we show that, in a normal metal system coupled to BCS superconductors, half-integer Levitons minimize the excess noise in the Andreev regime. Interestingly, energy-entangled electron states can be realized on-demand in this type of hybrid setup by exploiting crossed Andreev reflection. The results exposed in this review have potential applications in the context of quantum information and computation with single-electron flying qubits.