Seedless Cu Electroplating on Ru-W Thin Films for Metallisation of Advanced Interconnects.

For decades, Ta/TaN has been the industry standard for a diffusion barrier against Cu in interconnect metallisation. The continuous miniaturisation of transistors and interconnects into the nanoscale are pushing conventional materials to their physical limits and creating the need to replace them. Binary metallic systems, such as Ru-W, have attracted considerable attention as possible replacements due to a combination of electrical and diffusion barrier properties and the capability of direct Cu electroplating. The process of Cu electrodeposition on Ru-W is of fundamental importance in order to create thin, continuous, and adherent films for advanced interconnect metallisation. This work investigates the effects of the current density and application method on the electro-crystallisation behaviour of Cu. The film structure, morphology, and chemical composition were assessed by digital microscopy, atomic force microscopy, scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The results show that it was possible to form a thin Cu film on Ru-W with interfacial continuity for current densities higher than 5 mA·cm-2; however, the substrate regions around large Cu particles remained uncovered. Pulse-reverse current application appears to be more beneficial than direct current as it decreased the average Cu particle size.

Boat noise interferes with Lusitanian toadfish acoustic communication.

Anthropogenic noise is considered a major underwater pollutant as increasing ocean background noise due to human activities is impacting aquatic organisms. One of the most prevalent anthropogenic sounds is boat noise. Although motorboat traffic has increased in the past few decades, its impact on the communication of fish is still poorly known. The highly vocal Lusitanian toadfish (Halobatrachus didactylus) is an excellent model to test the impact of this anthropogenic stressor as it relies on acoustic communication to attract mates. Here, we performed two experiments to test the impact of boat noise on the acoustic communication of the Lusitanian toadfish. Using the auditory evoked potential (AEP) technique, we first compared the maximum distance a fish can perceive a boatwhistle (BW), the mate attraction acoustic signal, before and after embedding it in boat noise. Noises from a small motorboat and from a ferryboat reduced the active space from a control value of 6.4-10.4 m to 2.0-2.5 m and 6.3-6.7 m, respectively. In the second experiment we monitored the acoustic behaviour of breeding males exposed to boat noise playbacks and we observed an increase in the inter-onset interval of BWs and a disruption of the usual vocal interactions between singing males. These results demonstrate that boat noise can severely reduce the acoustic active space and affect the chorusing behaviour in this species, which may have consequences in breeding success for individuals and could thus affect fitness.

Microstructural Characterization of Carbon Nanotubes (CNTs)-Reinforced Nickel Matrix Nanocomposites.

This research focuses on the microstructural characterization of nickel matrix composites reinforced by carbon nanotubes (CNTs). The nanocomposites were produced by a conventional powder metallurgy process and the dispersion of CNTs and mixture with nickel powders was performed in a single step by ultrasonication. Microstructural characterization of Ni-CNT nanocomposites was performed by scanning and transmission electron microscopy, electron backscattered diffraction, high-resolution transmission electron microscopy, selected area electron diffraction, and fast Fourier transform analyses. This characterization revealed CNTs embedded in the nickel grains and mainly presented as clusters at the grain boundaries. CNTs hinder recrystallization during sintering, and dislocation cells and subgrains form as a result of the recovery process.

Microstructural Characterization of Aluminum-Carbon Nanotube Nanocomposites Produced Using Different Dispersion Methods.

This research focuses on characterization of the impact of dispersion methods on aluminum-carbon nanotubes (Al-CNTs) nanocomposite structure. Nanocomposites were produced by a conventional powder metallurgy process after the dispersion of the CNTs on the Al powders, using two approaches: (1) the dispersion of CNTs and mixture with Al powders were performed in a single step by ultrasonication; and (2) the CNTs were previously untangled by ultrasonication and then mixed with Al powders by ball milling. Microstructural characterization of Al-CNT nanocomposites was performed by optical microscopy, scanning and transmission electron microscopy, electron backscatter diffraction, and high-resolution transmission electron microscopy (HRTEM). Microstructural characterization revealed that the use of ball milling for mixing CNTs with Al powders promoted the formation of CNT clusters of reduced size, more uniformly dispersed in the matrix, and a nanocomposite of smaller grain size. However, the results of HRTEM and Raman spectroscopy show that ball milling causes higher damage to the CNT structure. The strengthening effect of the CNT is attested by the increase in hardness and tensile strength of the nanocomposites.

TEM and HRTEM characterization of TiAl diffusion bonds using Ni/Al nanolayers.

Diffusion bonding of TiAl alloys can be enhanced by the use of reactive nanolayer thin films as interlayers. Using these interlayers, it is possible to reduce the conventional bonding conditions (temperature, time, and pressure) and obtain sound and reliable joints. The microstructural characterization of the diffusion bond interfaces is a fundamental step toward understanding and identifying the bonding mechanisms and relating them to the strength of the joints. The interface of TiAl samples joined using Ni/Al nanolayers was characterized by transmission electron microscopy and scanning transmission electron microscopy. Microstructural characterization of the bond revealed that the interfaces consist of several thin layers of different composition and grain size (nanometric and micrometric). The bonding temperature (800, 900, or 1,000°C) determines the grain size and thickness of the layers present at the interface. Phase identification by high-resolution transmission electron microscopy combined with fast Fourier transform and electron energy-loss spectroscopy analyses reveals the presence of several intermetallic compounds: AlTiNi, NiAl, and Al2TiNi. For bonds produced at 800 and 900°C, nanometric grains of Ti were detected at the center of the interface.

Call recognition and individual identification of fish vocalizations based on automatic speech recognition: An example with the Lusitanian toadfish.

The study of acoustic communication in animals often requires not only the recognition of species specific acoustic signals but also the identification of individual subjects, all in a complex acoustic background. Moreover, when very long recordings are to be analyzed, automatic recognition and identification processes are invaluable tools to extract the relevant biological information. A pattern recognition methodology based on hidden Markov models is presented inspired by successful results obtained in the most widely known and complex acoustical communication signal: human speech. This methodology was applied here for the first time to the detection and recognition of fish acoustic signals, specifically in a stream of round-the-clock recordings of Lusitanian toadfish (Halobatrachus didactylus) in their natural estuarine habitat. The results show that this methodology is able not only to detect the mating sounds (boatwhistles) but also to identify individual male toadfish, reaching an identification rate of ca. 95%. Moreover this method also proved to be a powerful tool to assess signal durations in large data sets. However, the system failed in recognizing other sound types.

Acoustic fish community in the Madeira Archipelago (North Atlantic Ocean): Characterization of sound diversity and daily patterns.

Marine ecosystems are increasingly subjected to anthropogenic pressures, which demands urgent monitoring plans. Understanding soundscapes can offer unique insights into the ocean status providing important information and revealing different sounds and their sources. Fishes can be prominent soundscape contributors, making passive acoustic monitoring (PAM) a potential tool to detect the presence of vocal fish species and to monitor changes in biodiversity. The major goal of this research was to provide a first reference of the marine soundscapes of the Madeira Archipelago focusing on fish sounds, as a basis for a long-term PAM program. Based on the literature, 102 potentially vocal and 35 vocal fish species were identified. Additionally 43 putative fish sound types were detected in audio recordings from two marine protected areas (MPAs) in the Archipelago: the Garajau MPA and the Desertas MPA. The Garajau MPA exhibited higher fish vocal activity, a greater variety of putative fish sound types and higher fish sound diversity. Lower abundance of sounds was found at night at both MPAs. Acoustic activity revealed a clear distinction between diurnal and nocturnal fish groups and demonstrated daily patterns of fish sound activity, suggesting temporal and spectral partitioning of the acoustic space. Pomacentridae species were proposed as candidates for some of the dominant sound types detected during the day, while scorpionfishes (Scorpaena spp.) were proposed as sources for some of the dominant nocturnal fish sounds. This study provides an important baseline about this community acoustic behaviour and is a valuable steppingstone for future non-invasive and cost-effective monitoring programs in Madeira.

Origin and Early Evolution of Hydrocharitaceae and the Ancestral Role of Stratiotes.

The combined morphological features of Stratiotes (Hydrocharitaceae) pollen, observed with light and electron microscopy, make it unique among all angiosperm pollen types and easy to identify. Unfortunately, the plant is (and most likely was) insect-pollinated and produces relatively few pollen grains per flower, contributing to its apparent absence in the paleopalynological record. Here, we present fossil Stratiotes pollen from the Eocene of Germany (Europe) and Kenya (Africa), representing the first reliable pre-Pleistocene pollen records of this genus worldwide and the only fossils of this family discovered so far in Africa. The fossil Stratiotes pollen grains are described and compared to pollen from a single modern species, Stratiotes aloides L. The paleophytogeographic significance and paleoecological aspects of these findings are discussed in relation to the Hydrocharitaceae fossil records and molecular phylogeny, as well as the present-day distribution patterns of its modern genera.

Fused Filament Fabrication for Metallic Materials: A Brief Review.

Fused filament fabrication (FFF) is an extrusion-based additive manufacturing (AM) technology mostly used to produce thermoplastic parts. However, producing metallic or ceramic parts by FFF is also a sintered-based AM process. FFF for metallic parts can be divided into five steps: (1) raw material selection and feedstock mixture (including palletization), (2) filament production (extrusion), (3) production of AM components using the filament extrusion process, (4) debinding, and (5) sintering. These steps are interrelated, where the parameters interact with the others and have a key role in the integrity and quality of the final metallic parts. FFF can produce high-accuracy and complex metallic parts, potentially revolutionizing the manufacturing industry and taking AM components to a new level. In the FFF technology for metallic materials, material compatibility, production quality, and cost-effectiveness are the challenges to overcome to make it more competitive compared to other AM technologies, like the laser processes. This review provides a comprehensive overview of the recent developments in FFF for metallic materials, including the metals and binders used, the challenges faced, potential applications, and the impact of FFF on the manufacturing (prototyping and end parts), design freedom, customization, sustainability, supply chain, among others.

Adding Value to Secondary Aluminum Casting Alloys: A Review on Trends and Achievements.

Aluminum is a critical element of the circular economy as it can be recycled several times. Moreover, Al recycling is a more economically and environmentally efficient procedure than the primary Al production from ores. Secondary aluminum alloys are mostly used in casting applications since it is possible to accommodate their chemical composition through secondary manufacturing processes. However, the quality of the alloys may be considerably altered during the different steps of the recycling process. Inadequate waste sorting might result in excessive contamination. Iron is the most dangerous contaminant because it causes brittle and fragile intermetallic phases, which significantly impacts the mechanical characteristics of alloys. In addition, the microstructure of the alloy changes significantly after multiple cycles of remelting. These issues lead to the downcycling of aluminum, i.e., in other words, the reduction in the overall quality of the alloys. Thus, it has been shown that a number of procedures, including ultrasonic melt treatment and microalloying with rare earths, can somewhat alter the shape of the Fe-rich phases in order to reduce the shortcomings of downcycling. However, a solid mechanical characterization is still missing in order to improve the Fe-rich phase alteration.

Detection of invasive fish species with passive acoustics: Discriminating between native and non-indigenous sciaenids.

Invasive alien species have been rising exponentially in the last decades impacting biodiversity and ecosystem functioning. The soniferous weakfish, Cynoscion regalis, is a recent invasive sciaenid species in the Iberian Peninsula and was first reported in the Tagus estuary in 2015. There is concern about its possible impacts on native species, namely the confamiliar meagre, Argyrosomus regius, as there is overlap in their feeding regime, habitat use, and breeding behaviour. Here, we characterised the sciaenid-like sounds recently recorded in the Tagus estuary and showed that they are made by weakfish as they have similar numbers of pulses and pulse periods to the sounds made by captive breeding weakfish. We further demonstrate that breeding grunts from weakfish and the native sciaenid, recorded either in captivity or Tagus estuary, differ markedly in sound duration, number of pulses and pulse period in the two species, but overlap in their spectral features. Importantly, these differences are easily detected through visual and aural inspections of the recordings, making acoustic recognition easy even for the non-trained person. We propose that passive acoustic monitoring can be a cost-effective tool for in situ mapping of weakfish outside its natural distribution and an invaluable tool for early detection and to monitor its expansion.

Impact of anthropogenic noise on the survival and development of meagre (Argyrosomus regius) early life stages.

The growth of human populations has been driving an unprecedent and widespread increase in marine traffic, posing a real threat to marine biodiversity. Even though we are now aware of the negative effects of shipping noise exposure on fish, information about the impact on their early life stages continues to lack. Meagre (Argyrosomus regius) is a vocal fish that uses estuaries with high levels of anthropogenic noise pollution as both breeding areas and nurseries. Here, the effects of boat noise exposure on the development and survival of meagre larvae were studied. Embryos and larvae were exposed to either noise (boat noise playback) or control treatments (coils producing a similar electric field to the speakers) and hatching rate, survival rate, morphometric traits and stress-related biomarkers, at hatching and at 2 days-post-hatching (dph) were analyzed. Results showed no conclusive effects of the impact of boat noise playback, even though there was an increased lipid droplet consumption and a decrease in body depth at 2dph larvae under this stressor. The assessment of oxidative stress and energy metabolism-related biomarkers at hatching showed a marginal decrease in superoxide dismutase (SOD) activity and no changes in DNA damage or electron transport system activity (ETS), although it cannot be disregarded that those effects could only be visible at later stages of larval development. Whether these morphological and developmental results have implications in later stages remains to be investigated. Further studies with longer exposure and wild meagre could help deepen this knowledge and provide a better understanding of how anthropogenic noise can impact meagre early stages.

Study of ink paper sensor based on aluminum/carbon nanotubes agglomerated nanocomposites.

Agglomerated nanocomposites based on Aluminum/Carbon Nanotubes (AI/CNT) were produced by an arc discharge technique under argon/acetone atmosphere and ultrasonically dispersed in distilled water to form an ink-like composite. This ink was spread onto commercial paper to produce a conductive thick film. Experimental results show that the electrical resistance of Al/CNT nanocomposite on paper changes when a mechanical stress and/or heat is applied. The multi-sensory properties obtained are the following: (i) piezoresistive effect, electrical resistance shows linear dependence with pressure intensity at room temperature; (ii) polynomial relationship between electrical resistance and temperature; and (iii) high accuracy thermal sensor compared to a K type thermocouple at 25 degrees C. The nanocomposite and paper morphology was analyzed by Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM/EDS) and a favorable surface for physisorption was observed. Transmission Electron Microscopy (TEM) was utilized for Al/CNT agglomerated indicating that the ink paper based on nanocomposite shows good performance as a thermo-piezoresistive sensor.

Co-W Barrier Layers for Metallization of Copper Interconnects: Thermal Performance Analysis.

The back-end-of-line (BEOL) copper interconnect structure has been subjected to downscaling for the last two decades, while the materials used for conforming and assuring its physical integrity during processing have faced significant obstacles as the single-digit nanometer process node is implemented. In particular, the diffusion barrier layer system comprised of Ta/TaN has faced major constraints when it comes to the electrical performance of the smaller Cu lines, and thus alternative formulations have been investigated in recent years, such as Ru-Ta or Co-W alloys. In this work, we assess how PVD (physical vapor deposition) deposited equimolar Co-W films perform when exposed to different vacuum annealing temperatures and how these films compare with the Ta adhesion layer used for Cu seeding in terms of dewetting resistance. The stacks were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDX) mapping. The Cu film at the surface of the Cu/Co-W system exhibited grain growth starting at 300 °C, with the formation of abnormally large Cu grains starting at 450 °C. Sheet resistance reached a minimum value of 7.07 × 10-6 Ω/sq for the Cu/Co-W stack and 6.03 × 10-6 Ω/sq for the Cu/Ta stack, both for the samples annealed at 450 °C.

The Effect of Ultrasonic Agitation on the Seedless Growth of Cu on Ru-W Thin Films.

Ru attracted considerable attention as a candidate to replace TaN as a diffusion barrier layer for Cu interconnect metallisation. The addition of W improves the diffusion barrier properties of Ru but appears to weaken the adhesion strength between the barrier and Cu and the direct (seedless) electroplatability behaviour. Although Cu can be directly electroplated on near equimolar Ru-W thin films, no complete substrate coverage is obtained. The understanding of Cu electrocrystallisation on Ru−W is essential to develop methods of fabricating thin, continuous, and well adherent films for advanced interconnect metallisation, where Ru−W thin films could be used as diffusion barriers. This work studies the effect of ultrasonic agitation on the growth of Cu films electroplated on Ru−W, namely on the impact on substrate coverage. Film structure, morphology and chemical composition were evaluated by digital and scanning and transmission electron microscopies, and X-ray diffraction. The results show that Cu particles decrease with increasing current density, but when no electrolyte agitation is applied, substrate coverage is incomplete in the central region, with openings around larger Cu particles, regardless of current density. Under ultrasonic agitation, substrate coverage is remarkably improved. An active particle detachment mechanism is proposed as responsible for attaining improved substrate coverage, only possible at intermediate current density. Lower current densities promote growth over nucleation, whereas higher currents result in extensive hydrogen reduction/formation. Ultrasonic agitation also enhances a preferential Cu growth along <111> direction.

A Study on a Cast Steel Reinforced with WC-Metal Matrix Composite.

This study seeks to investigate the local reinforcement of low carbon cast steel specimens with WC-metal matrix composites (WC-MMCs), to obtain a new material effective in competing with hard alloy steels. For this purpose, a powder compact of tungsten carbide (WC) and iron (Fe) was prepared and placed in the mold cavity before casting. The reactions that occurred with the molten steel led to the formation of the WC-MMC and, consequently, to the local reinforcement of the steel. The microstructure of the WC-MMC reinforcement was characterized by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and electron backscatter diffraction (EBSD). The results showed a microstructural variation throughout the depth of the reinforcement. In the surface region, most of the original WC particles retain their polygonal morphology, but towards the base metal, the dissolution of the WC particles increased with the formation of (Fe,W)6C carbides. Closer to the base metal, dendritic eutectic carbides of (Fe,W)6C and fine (Fe,W)23C6 precipitates in a matrix of martensite were formed. The mechanical properties of the reinforcement were evaluated by hardness and ball-cratering abrasion tests. The results revealed a significant increase in hardness, being three times harder than the base metal, and a decrease of 39% in the wear rate.

Boat noise impacts Lusitanian toadfish breeding males and reproductive outcome.

Anthropogenic noise is a growing threat to marine organisms, including fish. Yet very few studies have addressed the impact of anthropogenic noise on fish reproduction, especially in situ. In this study, we investigated the impacts of boat noise exposure in the reproductive success of wild Lusitanian toadfish (Halobatrachus didactylus), a species that relies on advertisement calls for mate attraction, using behavioural, physiological and reproductive endpoints. Two sets of artificial nests were deployed in the Tagus estuary and exposed to either ambient sound or boat noise during their breeding season. Toadfish males spontaneously used these nests to breed. We inspected nests for occupation and the presence of eggs in six spring low tides (in two years) and assessed male vocal activity and stress responses. Boat noise did not affect nest occupation by males but impacted reproductive success by decreasing the likelihood of receiving eggs, decreasing the number of live eggs and increasing the number of dead eggs, compared to control males. Treatment males also showed depressed vocal activity and slightly higher cortisol levels. The assessment of oxidative stress and energy metabolism-related biomarkers revealed no oxidative damage in noise exposed males despite having lower antioxidant responses and pointed towards a decrease in the activity levels of energy metabolism-related biomarkers. These results suggest that males exposed to boat noise depressed their metabolism and their activity (such as parental care and mate attraction) to cope with an acoustic stressor, consistent with a freezing defensive response/behaviour. Together, our study demonstrates that boat noise has severe impacts on reproductive fitness in Lusitanian toadfish. We argue that, at least fishes that cannot easily avoid noise sources due to their dependence on specific spawning sites, may incur in significant direct fitness costs due to chronic noise exposure.

Production of TiC-MMCs Reinforcements in Cast Ferrous Alloys Using In Situ Methods.

This literature review aims to summarize the research conducted on the production of locally reinforced ferrous castings based on metal matrix composites reinforced with TiC (TiC-MMCs). One way to improve the wear resistance of cast components is to reinforce critical regions locally with metal matrix composites (MMCs) without changing the toughness of the component core. The in situ method of self-propagating high-temperature synthesis is one of the main approaches for the production of this enhanced material. Using this approach, the reinforcement is formed from a powder compact inserted in the mold cavity. The temperature of the liquid metal then produces the combustion reactions of the powders, which promote the formation of the ceramic phase. This paper focuses on eight powder systems used to synthesize TiC: Ti-C, Ni-Ti-C, Ni-Ti-B4C, Fe-Ti-C/Fe-Cr-Ti-C, Cu-Ti-B4C, Al-Ti-C, and Al-Ti-B4C, and provides an overview of the methodologies used as well as the effect of processing variables on the microstructural and mechanical characteristics of the reinforcement zones.

Boat noise affects meagre (Argyrosomus regius) hearing and vocal behaviour.

Aquatic noise has increased in last decades imposing new constraints on aquatic animals' acoustic communication. Meagre (Argyrosomus regius) produce loud choruses during the breeding season, likely facilitating aggregations and mating, and are thus amenable to being impacted by anthropogenic noise. We assessed the impact of boat noise on this species acoustic communication by: evaluating possible masking effects of boat noise on hearing using Auditory Evoked Potentials (AEP) and inspecting changes in chorus sound levels from free ranging fish upon boat passages. Our results point to a significant masking effect of anthropogenic noise since we observed a reduction of ca. 20 dB on the ability to discriminate conspecific calls when exposed to boat noise. Furthermore, we verified a reduction in chorus energy during ferryboat passages, a behavioural effect that might ultimately impact spawning. This study is one of few addressing the effects of boat noise by combining different methodologies both in the lab and with free ranging animals.