Tantalum-based diffusion barriers for copper metallization

Interfacial reactions between Cu and Si with different Ta-based diffusion barriers are investigated by means of the combined thermodynamic-kinetic and microstructural analysis. The reaction mechanisms and the related microstructures in the Si/Ta/Cu, Si/TaC/Cu and Si/Ta2N/Cu metallization systems are studied experimentally and theoretically by utilizing the ternary Si-Ta-Cu, Si-Ta-C, Si-Ta-N, Ta-C-Cu, and Ta-N-Cu phase diagrams as well as the activity diagrams calculated at different temperatures. The effects of oxygen on the reactions in the Si/Ta/Cu and Si/TaC/Cu metallization systems are investigated by employing also the evaluated Ta-O and Ta-C-O phase diagrams. The experimental investigations are carried out with the help of sheet resistance measurements, x-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), scanning electron microscopy (SEM), secondary ion mass spectroscopy (SIMS) and transmission electron microscopy (TEM). It is shown that by using the combined thermodynamic-kinetic approach a better understanding about the reactions taking place in the Si/Cu diffusion couples with different Ta-based diffusion barriers can be achieved. The diffusion barrier solutions using Ta are good candidates for practical applications.reviewe

Simultaneous electrochemical detection of tramadol and O-desmethyltramadol with Nafion-coated tetrahedral amorphous carbon electrode

Tramadol (TR) is a member of the opioid family and is widely used for pain treatment in clinical patient care. The analgesic effect of tramadol is induced primarily by its main metabolite Odesmethyltramadol (ODMT). Due to interindividual differences in the TR metabolism to ODMT, the responses to TR vary highly between patients. Thus, a fast and selective method for simultaneous detection of TR and ODMT would increase the patient safety and pain treatment efficacy. In this study, a tetrahedral amorphous carbon (ta-C) electrode coated with a thin dip-coated recast Nafion membrane was fabricated for selective electrochemical determination of TR and ODMT. With this Nafion/ta-C electrode, simultaneous detection of TR and ODMT was achieved with linear ranges of 1-12.5 mu M and 1-15 mu M, respectively. The limits of detection were 131 nM for TR and 209 nM for ODMT. Both analytes were also measured in the presence of several common interferents, demonstrating the high selectivity of the fabricated electrode. In addition, the effect of pH on the peak potential was studied to observe the electrochemical behavior of the analytes at the electrode. Finally, clinically relevant concentrations of TR and ODMT were simultaneously detected from diluted human plasma to assess the applicability of the electrode in real samples. The fabricated Nafion/ta-C electrode was found successful in the simultaneous electrochemical detection of TR and ODMT in both buffer solution and in human plasma. (C) 2018 Elsevier Ltd. All rights reserved.Peer reviewe

Selective detection of morphine in the presence of paracetamol with anodically pretreated dual layer Ti/tetrahedral amorphous carbon electrodes

We investigated the effect of anodic treatment of titanium/tetrahedral amorphous carbon electrodes on the electrochemical detection of morphine and paracetamol. The anodic treatment caused both oxidation of the carbon and, more importantly, exposure and oxidation of the underlying Ti layer. This treatment anodically shifted the oxidation potential of paracetamol while that of morphine remained unaffected. The resulting electrode also showed better selectivity than a ta-C electrode without Ti. After anodic treatment at 2.5 V, selective detection of morphine with a physiologically meaningful detection limit of 9.8 nM and a linear range of 0.1-10 mu M was obtained in the presence of 100 mu M paracetamol.Peer reviewe

Growth Mechanism and Origin of High sp^{3} Content in Tetrahedral Amorphous Carbon.

We study the deposition of tetrahedral amorphous carbon (ta-C) films from molecular dynamics simulations based on a machine-learned interatomic potential trained from density-functional theory data. For the first time, the high sp^{3} fractions in excess of 85% observed experimentally are reproduced by means of computational simulation, and the deposition energy dependence of the film's characteristics is also accurately described. High confidence in the potential and direct access to the atomic interactions allow us to infer the microscopic growth mechanism in this material. While the widespread view is that ta-C grows by "subplantation," we show that the so-called "peening" model is actually the dominant mechanism responsible for the high sp^{3} content. We show that pressure waves lead to bond rearrangement away from the impact site of the incident ion, and high sp^{3} fractions arise from a delicate balance of transitions between three- and fourfold coordinated carbon atoms. These results open the door for a microscopic understanding of carbon nanostructure formation with an unprecedented level of predictive power.This research was financially supported by the Academy of Finland through Grants No. 310574 and No. 285526. Computational resources were provided by CSC—IT Center for Science, Finland, though Projects No. 2000634 and No. 2000300. V. L. D. gratefully acknowledges a fellowship from the Alexander von Humboldt Foundation, a Leverhulme Early Career Fellowship, and support from the Isaac Newton Trust

Nanoscale geometry determines mechanical biocompatibility of vertically aligned nanofibers

Vertically aligned carbon nanofibers (VACNFs) are promising material candidates for neural biosensors due to their ability to detect neurotransmitters in physiological concentrations. However, the expected high rigidity of CNFs could induce mechanical mismatch with the brain tissue, eliciting formation of a glial scar around the electrode and thus loss of functionality. We have evaluated mechanical biocompatibility of VACNFs by growing nickel-catalyzed carbon nanofibers of different lengths and inter-fiber distances. Long nanofibers with large inter-fiber distance prevented maturation of focal adhesions, thus constraining cells from obtaining a highly spread morphology that is observed when astrocytes are being contacted with stiff materials commonly used in neural implants. A silicon nanopillar array with 500 nm inter-pillar distance was used to reveal that this inhibition of focal adhesion maturation occurs due to the surface nanoscale geometry, more precisely the inter-fiber distance. Live cell atomic force microscopy was used to confirm astrocytes being significantly softer on the long Ni-CNFs compared to other surfaces, including a soft gelatin hydrogel. We also observed hippocampal neurons to mature and form synaptic contacts when being cultured on both long and short carbon nanofibers, without having to use any adhesive proteins or a glial monoculture, indicating high cytocompatibility of the material also with neuronal population. In contrast, neurons cultured on a planar tetrahedral amorphous carbon sample showed immature neurites and indications of early-stage apoptosis. Our results demonstrate that mechanical biocompatibility of biomaterials is greatly affected by their nanoscale surface geometry, which provides means for controlling how the materials and their mechanical properties are perceived by the cells.Peer reviewe

Protein Adsorption and Its Effects on Electroanalytical Performance of Nanocellulose/Carbon Nanotube Composite Electrodes

Protein fouling is a critical issue in the development of electrochemical sensors for medical applications, as it can significantly impact their sensitivity, stability, and reliability. Modifying planar electrodes with conductive nanomaterials that possess a high surface area, such as carbon nanotubes (CNTs), has been shown to significantly improve fouling resistance and sensitivity. However, the inherent hydrophobicity of CNTs and their poor dispersibility in solvents pose challenges in optimizing such electrode architectures for maximum sensitivity. Fortunately, nanocellulosic materials offer an efficient and sustainable approach to achieving effective functional and hybrid nanoscale architectures by enabling stable aqueous dispersions of carbon nanomaterials. Additionally, the inherent hygroscopicity and fouling-resistant nature of nanocellulosic materials can provide superior functionalities in such composites. In this study, we evaluate the fouling behavior of two nanocellulose (NC)/multiwalled carbon nanotube (MWCNT) composite electrode systems: one using sulfated cellulose nanofibers and another using sulfated cellulose nanocrystals. We compare these composites to commercial MWCNT electrodes without nanocellulose and analyze their behavior in physiologically relevant fouling environments of varying complexity using common outer- and inner-sphere redox probes. Additionally, we use quartz crystal microgravimetry with dissipation monitoring (QCM-D) to investigate the behavior of amorphous carbon surfaces and nanocellulosic materials in fouling environments. Our results demonstrate that the NC/MWCNT composite electrodes provide significant advantages for measurement reliability, sensitivity, and selectivity over only MWCNT-based electrodes, even in complex physiological monitoring environments such as human plasma.</p

New electrochemically improved tetrahedral amorphous carbon films for biological applications

Carbon based materials have been frequently used to detect different biomolecules. For example high sp3 containing hydrogen free diamond-like carbon (DLC) possesses many properties that are beneficial for biosensor applications. Unfortunately, the sensitivities of the DLC electrodes are typically low. Here we demonstrate that by introducing topography on the DLC surface and by varying its layer thickness, it is possible to significantly increase the sensitivity of DLC thin film electrodes towards dopamine. The electrode structures are characterized in detail by atomic force microscopy (AFM) and conductive atomic force microscopy (C-AFM) as well as by transmission electron microscopy (TEM) combined with electron energy loss spectroscopy (EELS). With cyclic voltammetry (CV) measurements we demonstrate that the new improved DLC electrode has a very wide water window, but at the same time it also exhibits fast electron transfer rate at the electrode/solution interface. In addition, it is shown that the sensitivity towards dopamine is increased up to two orders of magnitude in comparison to the previously fabricated DLC films, which are used as benchmarks in this investigation. Finally, it is shown, based on the cyclic voltammetry measurements that dopamine exhibits highly complex behavior on top of these carbon electrodes.The authors T.L, V.P., S.S., T.P., and J.K., would like to acknowledge the National Agency for Technology and Innovation (grant number 211488) and Aalto University (grant number 902380) for the financial support

Integrity of APS, HVOF and HVAF sprayed NiCr and NiCrBSi coatings based on the tensile stress-strain response

The interlamellar cohesion of thermal spray coatings influences greatly their mechanical properties and ability to use coatings in different loading conditions and wear/erosion resistance. In the present study, micro-tensile testing of free-standing coatings was utilized to evaluate the mechanical response of thermally sprayed coatings. In addition, the longitudinal uniaxial fracture strength of free-standing coatings could be determined by a tensile test. The coating materials studied were NiCr and NiCrBSi coatings sprayed by atmospheric plasma spraying (APS), high velocity oxy-fuel (HVOF), and high velocity air-fuel (HVAF) processes. The different materials used for the coatings sprayed by different methods yield different microstructures, different stress-strain relation in tensile testing. Different tensile test response was found to be related to cohesion strength between lamellas, and thus was affecting the cavitation erosion wear. The effect of other factors such as hardness and residual stresses on cavitation resistance were also discussed. Such results are crucial to understand the suitability of microstructures obtained by TS processes for different wear conditions.publishedVersionPeer reviewe