How to catch a shear band and explain plasticity of metallic glasses with continuum mechanics.

Capturing a shear band in a metallic glass during its propagation experimentally is very challenging. Shear bands are very narrow but extend rapidly over macroscopic distances, therefore, characterization of large areas at high magnification and high speed is required. Here we show how to control the shear bands in a pre-structured thin film metallic glass in order to directly measure local strains during initiation, propagation, or arrest events. Based on the experimental observations, a model describing the shear banding phenomenon purely within the frameworks of continuum mechanics is formulated. We claim that metallic glasses exhibit an elastic limit of about 5% which must be exceeded locally either at a stress concentrator to initiate a shear banding event, or at the tip of a shear band during its propagation. The model can successfully connect micro- and macroscopic plasticity of metallic glasses and suggests an alternative interpretation of controversial experimental observations.

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.

The Roles of Impurities and Surface Area on Thermal Stability and Oxidation Resistance of BN Nanoplatelets.

This study considers the influence of purity and surface area on the thermal and oxidation properties of hexagonal boron nitride (h-BN) nanoplatelets, which represent crucial factors in high-temperature oxidizing environments. Three h-BN nanoplatelet-based materials, synthesized with different purity levels and surface areas (~3, ~56, and ~140 m2/g), were compared, including a commercial BN reference. All materials were systematically analyzed by various characterization techniques, including gas pycnometry, scanning electron microscopy, X-ray diffraction, Fourier-transform infrared radiation, X-ray photoelectron spectroscopy, gas sorption analysis, and thermal gravimetric analysis coupled with differential scanning calorimetry. Results indicated that the thermal stability and oxidation resistance of the synthesized materials were improved by up to ~13.5% (or by 120 °C) with an increase in purity. Furthermore, the reference material with its high purity and low surface area (~4 m2/g) showed superior performance, which was attributed to the minimized reactive sites for oxygen diffusion due to lower surface area availability and fewer possible defects, highlighting the critical roles of both sample purity and accessible surface area in h-BN thermo-oxidative stability. These findings highlight the importance of focusing on purity and surface area control in developing BN-based nanomaterials, offering a path to enhance their performance in extreme thermal and oxidative conditions.

Short-Time Magnetron Sputtering for the Development of Carbon-Palladium Nanocomposites.

In recent nanomaterials research, combining nanoporous carbons with metallic nanoparticles, like palladium (Pd), has emerged as a focus due to their potential in energy, environmental and biomedical fields. This study presents a novel approach for synthesizing Pd-decorated carbons using magnetron sputter deposition. This method allows for the functionalization of nanoporous carbon surfaces with Pd nano-sized islands, creating metal-carbon nanocomposites through brief deposition times of up to 15 s. The present research utilized direct current magnetron sputtering to deposit Pd islands on a flexible activated carbon cloth substrate. The surface chemistry, microstructure, morphology and pore structure were analyzed using a variety of material characterization techniques, including X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectroscopy, gas sorption analysis and scanning electron microscopy. The results showed Pd islands of varying sizes distributed across the cloth's carbon fibers, achieving high-purity surface modifications without the use of chemicals. The synthesis method preserves the nanoporous structure of the carbon cloth substrate while adding functional Pd islands, which could be potentially useful in emerging fields like hydrogen storage, fuel cells and biosensors. This approach demonstrates the possibility of creating high-quality metal-carbon composites using a simple, clean and economical method, expanding the possibilities for future nanomaterial-based applications.

Nanoporous Carbon Electrodes Derived from Coffee Side Streams for Supercapacitors in Aqueous Electrolytes.

Coffee, as one of the most traded resources, generates a vast amount of biogenic by-products. Coffee silver skins (CSS), a side stream from the roasting process, account for about 4 wt.%. Despite the abundancy of CSS, possible routes to generate added value for broad applications are limited. Herein, we present an approach to use CSS as a precursor material for supercapacitor electrodes. KOH activated carbon (AC) was produced from CSS. The resulting AC-CSS was characterized by X-ray diffraction, gas sorption analysis, scanning electron microscopy, and Raman spectroscopy. The highly porous AC-CSS exposes a specific surface area of more than 2500 m2 g-1. Electrodes formed with AC-CSS were electrochemically characterized by performing cyclic voltammetry and galvanostatic cycling. The electrodes were further assembled into a supercapacitor device and operated using 1 M sulfuric acid as electrolyte. In addition, various quinones were added to the electrolyte and their impact on the capacitance of AC-CSS electrodes was analyzed. In this work, we were able to show that CSS are a valuable source for supercapacitor applications and that coffee-waste-derived quinones can act as capacitance enhancers. Thus, the findings of this research show a valuable path towards sustainable and green energy storage solutions.

Materials Engineering for Flexible Metallic Thin Film Applications.

More and more flexible, bendable, and stretchable sensors and displays are becoming a reality. While complex engineering and fabrication methods exist to manufacture flexible thin film systems, materials engineering through advanced metallic thin film deposition methods can also be utilized to create robust and long-lasting flexible devices. In this review, materials engineering concepts as well as electro-mechanical testing aspects will be discussed for metallic films. Through the use of residual stress, film thickness, or microstructure tailoring, all controlled by the film deposition parameters, long-lasting flexible film systems in terms of increased fracture or deformation strains, electrical or mechanical reliability, can be generated. These topics, as well as concrete examples, will be discussed. One objective of this work is to provide a toolbox with sustainable and scalable methods to create robust metal thin films for flexible, bendable, and stretchable applications.

Microstructural Effects on the Interfacial Adhesion of Nanometer-Thick Cu Films on Glass Substrates: Implications for Microelectronic Devices.

Improving the interface stability for nanosized thin films on brittle substrates is crucial for technological applications such as microelectronics because the so-called brittle-ductile interfaces limit their overall reliability. By tuning the thin film properties, interface adhesion can be improved because of extrinsic toughening mechanisms during delamination. In this work, the influence of the film microstructure on interface adhesion was studied on a model brittle-ductile interface consisting of nanosized Cu films on brittle glass substrates. Therefore, 110 nm thin Cu films were deposited on glass substrates using magnetron sputtering. While film thickness, residual stresses, and texture of the Cu films were maintained comparable in the sputtering processes, the film microstructure was varied during deposition and via isothermal annealing, resulting in four different Cu films with bimodal grain size distributions. The interface adhesion of each Cu film was then determined using stressed Mo overlayers, which triggered Cu film delaminations in the shape of straight, spontaneous buckles. The mixed-mode adhesion energy for each film ranged from 2.35 J/m2 for the films with larger grains to 4.90 J/m2 for the films with the highest amount of nanosized grains. This surprising result could be clarified using an additional study of the buckles using focused ion beam cutting and quantification via confocal laser scanning microscopy to decouple and quantify the amount of elastic and plastic deformation stored in the buckled thin film. It could be shown that the films with smaller grains exhibit the possibility of absorbing a higher amount of energy during delamination, which explains their higher adhesion energy.

Boron Nitride Nanotubes Versus Carbon Nanotubes: A Thermal Stability and Oxidation Behavior Study.

Nanotubes made of boron nitride (BN) and carbon have attracted considerable attention within the literature due to their unique mechanical, electrical and thermal properties. In this work, BN and carbon nanotubes, exhibiting high purity (>99%) and similar surface areas (~200 m2/g), were systematically investigated for their thermal stability and oxidation behavior by combining thermal gravimetric analysis and differential scanning calorimetry methods at temperatures of up to ~1300 °C under a synthetic air flow environment. The BN nanotubes showed a good resistance to oxidation up to ~900 °C and fully transformed to boron oxide up to ~1100 °C, while the carbon nanotubes were stable up to ~450 °C and almost completely combusted up to ~800 °C. The different oxidation mechanisms are attributed to the different chemical nature of the two types of nanotubes.

Molecular Coverage Determines Sliding Wear Behavior of n-Octadecylphosphonic Acid Functionalized Cu-O Coated Steel Disks against Aluminum.

The sliding wear behavior of Cu-O coated steel disks functionalized with n-octadecyl-phosphonic acids was evaluated against aluminum in ball-on-disk tribometer experiments. After 5 m of sliding the friction coefficient of the functionalized sample with maximum molecular coverage is ≤0.3 ± 0.1. Surfaces with lower coverage mitigate friction and wear as well exhibiting initially similar low friction coefficients but reveal the breakdown of lubrication for sliding distances <5 m. The length of the low friction sliding distance before breakdown scales with the coverage of n-octadecylphosphonic acids on the Cu-O surface. Coverage hence determines the tribological behavior of the functionalized surface against sliding aluminum. As the coverage is increased, detrimental asperity contacts between the rubbing surfaces are reduced.

Exceptional fracture resistance of ultrathin metallic glass films due to an intrinsic size effect.

Metallic glasses typically fail in a brittle manner through shear band propagation but can exhibit significant ductility when the sample size is reduced below a few hundreds of nanometers. To date the size effect was mainly demonstrated for free-standing samples and the role of extrinsic setup parameters on the observed behavior is still under debate. Therefore, in the present work we investigated the mechanical properties of polymer-supported sputtered amorphous Pd82Si18 thin films with various thicknesses. We show that the films exhibit brittle fracture for thicknesses far below 100 nm. A pronounced size effect resulting in extended crack-free deformation up to 6% strain was observed only in films as thin as 7 nm - a thickness which is lower than the typical shear band thickness. This size effect results in exceptional cyclic reliability of ultrathin metallic glass films which can sustain cyclic strains of 3% up to at least 30,000 cycles without any indication of fatigue damage or electrical conductivity degradation. Since the enhancement of mechanical properties is observed at ambient conditions using inexpensive substrates and an industrially scalable sputter deposition technique, a new research avenue for utilization of ultrathin metallic glasses in microelectronics, flexible electronics or nanoelectromechanical devices is opened up.

Antibacterial Silicon Oxide Thin Films Doped with Zinc and Copper Grown by Atmospheric Pressure Plasma Chemical Vapor Deposition.

Zn-doped and Cu-doped SiOx films were synthesized by atmospheric pressure plasma chemical vapor deposition to study their antibacterial efficiency against Gram-negative Escherichia coli and their cytotoxic effect on the growth of mouse cells. Zn-rich and Cu-rich particles with diameters up to several microns were found to be homogeneously distributed within the SiOx films. For both doping elements, bacteria are killed within the first three hours after exposure to the film surface. In contrast, mouse cells grow well on the surfaces of both film types, with a slight inhibition present only after the first day of exposure. The obtained results indicate that the films show a high potential for use as effective antibacterial surfaces for medical applications.

Enhanced Ti0.84Ta0.16N diffusion barriers, grown by a hybrid sputtering technique with no substrate heating, between Si(001) wafers and Cu overlayers.

We compare the performance of conventional DC magnetron sputter-deposited (DCMS) TiN diffusion barriers between Cu overlayers and Si(001) substrates with Ti0.84Ta0.16N barriers grown by hybrid DCMS/high-power impulse magnetron sputtering (HiPIMS) with substrate bias synchronized to the metal-rich portion of each pulse. DCMS power is applied to a Ti target, and HiPIMS applied to Ta. No external substrate heating is used in either the DCMS or hybrid DCMS/HiPIMS process in order to meet future industrial thermal-budget requirements. Barrier efficiency in inhibiting Cu diffusion into Si(001) while annealing for 1 hour at temperatures between 700 and 900 °C is investigated using scanning electron microscopy, X-ray diffraction, four-point-probe sheet resistance measurements, transmission electron microscopy, and energy-dispersive X-ray spectroscopy profiling. Ti0.84Ta0.16N barriers are shown to prevent large-scale Cu diffusion at temperatures up to 900 °C, while conventional TiN barriers fail at ≤700 °C. The improved performance of the Ti0.84Ta0.16N barrier is due to film densification resulting from HiPIMS pulsed irradiation of the growing film with synchronized Ta ions. The heavy ion bombardment dynamically enhances near-surface atomic mixing during barrier-layer deposition.

Deformation behavior of Re alloyed Mo thin films on flexible substrates: In situ fragmentation analysis supported by first-principles calculations.

A major obstacle in the utilization of Mo thin films in flexible electronics is their brittle fracture behavior. Within this study, alloying with Re is explored as a potential strategy to improve the resistance to fracture. The sputter-deposited Mo1-xRex films (with 0 ≤ x ≤ 0.31) were characterized in terms of structural and mechanical properties, residual stresses as well as electrical resistivity. Their deformation behavior was assessed by straining 50 nm thin films on polyimide substrates in uniaxial tension, while monitoring crack initiation and propagation in situ by optical microscopy and electrical resistance measurements. A significant toughness enhancement occurs with increasing Re content for all body-centered cubic solid solution films (x ≤ 0.23). However, at higher Re concentrations (x > 0.23) the positive effect of Re is inhibited due to the formation of dual-phase films with the additional close packed A15 Mo3Re phase. The mechanisms responsible for the observed toughness behavior are discussed based on experimental observations and electronic structure calculations. Re gives rise to both increased plasticity and bond strengthening in these Mo-Re solid solutions.

In-situ Observation of Cross-Sectional Microstructural Changes and Stress Distributions in Fracturing TiN Thin Film during Nanoindentation.

Load-displacement curves measured during indentation experiments on thin films depend on non-homogeneous intrinsic film microstructure and residual stress gradients as well as on their changes during indenter penetration into the material. To date, microstructural changes and local stress concentrations resulting in plastic deformation and fracture were quantified exclusively using numerical models which suffer from poor knowledge of size dependent material properties and the unknown intrinsic gradients. Here, we report the first in-situ characterization of microstructural changes and multi-axial stress distributions in a wedge-indented 9 µm thick nanocrystalline TiN film volume performed using synchrotron cross-sectional X-ray nanodiffraction. During the indentation, needle-like TiN crystallites are tilted up to 15 degrees away from the indenter axis in the imprint area and strongly anisotropic diffraction peak broadening indicates strain variation within the X-ray nanoprobe caused by gradients of giant compressive stresses. The morphology of the multiaxial stress distributions with local concentrations up to -16.5 GPa correlate well with the observed fracture modes. The crack growth is influenced decisively by the film microstructure, especially by the micro- and nano-scopic interfaces. This novel experimental approach offers the capability to interpret indentation response and indenter imprint morphology of small graded nanostructured features.

Temperature-dependent wear mechanisms for magnetron-sputtered AlTiTaN hard coatings.

AlTiTaN coatings have been demonstrated to have high thermal stability at temperatures up to 900 °C. It has been speculated that the high oxidation resistance promotes an improved wear resistance, specifically for dry machining applications. This work reports on the influence of temperature up to 900 °C on the wear mechanisms of AlTiTaN hard coatings. DC magnetron-sputtered coatings were obtained from an Al(46)Ti(42)Ta(12) target, keeping the substrate bias at -100 V and the substrate temperature at 265 °C. The coatings exhibited a single-phase face-centered cubic AlTiTaN structure. The dry sliding tests revealed predominant abrasion and tribo-oxidation as wear mechanisms, depending on the wear debris formed. At room temperature, abrasion leading to surface polishing was observed. At 700 and 800 °C, slow tribo-oxidation and an amorphous oxide formed reduced the wear rate of the coating compared to room temperature. Further, an increase in temperature to 900 °C increased the wear rate significantly due to fast tribo-oxidation accompanied by grooving. The friction coefficient was found to decrease with temperature increasing from 700 to 900 °C due to the formation of oxide scales, which reduce adhesion of asperity contacts. A relationship between the oxidation and wear mechanisms was established using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, surface profilometry, confocal microscopy, and dynamic secondary ion mass spectrometry.

N-K electron energy-loss near-edge structures for TiN/VN layers: an ab initio and experimental study.

We study N-K-edge electron energy-loss near-edge structures for well-defined TiN/VN bilayers grown on a MgO(100) substrate by both calculations and experiments. The structural relaxations and the electronic structure of TiN/VN multilayers are calculated using the Vienna Ab Initio Simulation Package computer code, which uses density functional theory to describe the electronic interaction. The effects of the core hole created in the excitation process are included in the calculations. For VN, off-stoichiometric effects due to nitrogen vacancies are modelled. The partial density of states (PDOS) for the N-K edge of atoms in the vicinity of the TiN/MgO interface revealed that two new peaks appear between 7 and 9 eV instead of a broad shoulder typical for the bulk. For the VN/TiN interface, the PDOS is modified only slightly, owing to similar bonding on both sides of the interface, and is thus very similar to the respective bulk spectra. An experimental spectrum taken at the VN/TiN interface is, however, well described by an average of the simulated spectra for VN and TiN bulk (interface). Such a finding is characteristic of an intermixed interface.