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.

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.

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.

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.

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.

Production and Characterization of Austenitic Stainless Steel Cast Parts Reinforced with WC Particles Fabricated by Ex Situ Technique.

In this work, austenitic stainless steel specimens were locally reinforced with WC particles. The reinforcements were fabricated via an ex situ technique based on powder technology. Mixtures of WC, Fe, and M0101 binder were cold-pressed to obtain powder compacts. After debinding and sintering, the porous WC-Fe inserts were fixed in a mold cavity, where they reacted with liquid metal. Microstructural analysis was conducted for characterization of the phases constituting the produced reinforcement zone and the bonding interface. The results revealed that the reinforcement is a graded material with compositional and microstructural gradients throughout its thickness. The zone nearest to the surface has a ferrous matrix with homogeneously distributed WC particles and (Fe,W,Cr)6C and (Fe,W,Cr)3C carbides, formed from the liquid metal reaction with the insert. This precipitation leads to austenite destabilization, which transforms into martensite during cooling. A vast dissolution of the WC particles occurred in the inner zones, resulting in more intense carbides formation. Cr-rich carbides ((Fe,Cr,W)7C3, and (Fe,Cr,W)23C6) formed in the interdendritic regions of austenite; this zone is characterized by coarse dendrites of austenite and a multi-phase interdendritic network composed of carbides. An interface free of discontinuities and porosities indicates good bonding of the reinforcement zone to stainless steel.

Seedless Cu Electroplating on Co-W Thin Films in Low pH Electrolyte: Early Stages of Formation.

The use of Ta/TaN barrier bilayer systems in electronic applications has been ubiquitous over the last decade. Alternative materials such as Co-W or Ru-W alloys have gathered interest as possible replacements due to their conjugation of favourable electrical properties and barrier layer efficiency at reduced thicknesses while enabling seedless Cu electroplating. The microstructure, morphology, and electrical properties of Cu films directly electrodeposited onto Co-W or Ru-W are important to assess, concomitant with their ability to withstand the electroplating baths/conditions. This work investigates the effects of the current application method and pH value of the electroplating solution on the electrocrystallisation behaviour of Cu deposited onto a Co-W barrier layer. The film structure, morphology, and chemical composition were studied by X-ray diffraction, scanning electron microscopy and atomic force microscopy, as well as photoelectron spectroscopy. The results show that the electrolyte solution at pH 1.8 is incapable of creating a compact Cu film over the Co-W layer in either pulsed or direct-current modes. At higher pH, a continuous film is formed. A mechanism is proposed for the nucleation and growth of Cu on Co-W, where a balance between Cu nucleation, growth, and preferential Co dissolution dictates the substrate area coverage and compactness of the electrodeposited films.

Preparation and Microstructural Characterization of a High-Cr White Cast Iron Reinforced with WC Particles.

High-chromium white cast iron (WCI) specimens locally reinforced with WC-metal matrix composites were produced via an ex situ technique: powder mixtures of WC and Fe cold-pressed in a pre-form were inserted in the mold cavity before pouring the base metal. The microstructure of the resulting reinforcement is a matrix of martensite (α') and austenite (γ) with WC particles evenly distributed and (Fe,W,Cr)6C carbides that are formed from the reaction between the molten metal and the inserted pre-form. The (Fe,W,Cr)6C precipitation leads to the hypoeutectic solidification of the matrix and the final microstructure consists of martensite, formed from primary austenite during cooling and eutectic constituent with (Fe,Cr)7C3 and (Fe,W,Cr)6C carbides. The presence of a reaction zone with 200 µm of thickness, between the base metal and the composite should guarantee a strong bonding between these two zones.

Microstructural Characterization of TiC-White Cast-Iron Composites Fabricated by In Situ Technique.

High-chromium white cast-iron specimens locally reinforced with TiC-metal matrix composites were successfully produced via an in situ technique based on combustion synthesis. Powder mixtures of Ti, Al, and graphite were prepared and compressed to fabricate green powder compacts that were inserted into the mold cavity before the casting. The heat of the molten iron causes the ignition of the combustion reaction of the reactant powders, resulting in the formation of the TiC by self-propagating high-temperature synthesis. The microstructure of the resultant composites and the bonding interfaces was characterized by scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The microstructural results showed a good adhesion of the composite, suggesting an effective infiltration of the metal into the inserted compact, yet a non-homogeneous distribution of the TiC in the martensite matrix was observed. Based on the results, the in situ synthesis appears to be a great potential technique for industrial applications.

EBSD Analysis of Metal Matrix Nanocomposite Microstructure Produced by Powder Metallurgy.

The development of metal nanocomposites reinforced by carbon nanotubes (CNTs) remains a focus of the scientific community due to the growing need to produce lightweight advanced materials with unique mechanical properties. However, for the successful production of these nanocomposites, there is a need to consolidate knowledge about how reinforcement influences the matrix microstructure and which are the strengthening mechanisms promoting the best properties. In this context, this investigation focuses on the study of the reinforcement effect on the microstructure of an Ni-CNT nanocomposites produced by powder metallurgy. The microstructural evolution was analysed by electron backscattered diffraction (EBSD). The EBSD results revealed that the dispersion/mixing and pressing processes induce plastic deformation in the as-received powders. The dislocation structures produced in those initial steps are partially eliminated in the sintering process due to the activation of recovery and recrystallization mechanisms. However, the presence of CNTs in the matrix has a significant effect on the dislocation annihilation, thus reducing the recovery of the dislocation structures.