Interfacial Compatibility in Microelectronics: Moving Away from the Trial and Error Approach

Interfaces between dissimilar materials are met everywhere in microelectronics and microsystems. In order to ensure faultless operation of these highly sophisticated structures, it is mandatory to have fundamental understanding of materials and their interactions in the system. In this difficult task, the “traditional” method of trial and error is not feasible anymore; it takes too much time and repeated efforts. In Interfacial Compatibility in Microelectronics, an alternative approach is introduced. In this revised method four fundamental disciplines are combined: i) thermodynamics of materials ii) reaction kinetics iii) theory of microstructures and iv) stress and strain analysis. The advantages of the method are illustrated in Interfacial Compatibility in Microelectronics which includes: •solutions to several common reliability issues in microsystem technology, •methods to understand and predict failure mechanisms at interfaces between dissimilar materials and •an approach to DFR based on deep understanding in materials science, rather than on the use of mechanistic tools, such as FMEA. Interfacial Compatibility in Microelectronics provides a clear and methodical resource for graduates and postgraduates alike.  

Connection between the physicochemical characteristics of amorphous carbon thin films and their electrochemical properties

Abstract Connecting a material's surface chemistry with its electrocatalytic performance is one of the major questions in analytical electrochemistry. This is especially important in many sensor applications where analytes from complex media need to be measured. Unfortunately, today this connection is still largely missing except perhaps for the most simple ideal model systems. Here we present an approach that can be used to obtain insights about this missing connection and apply it to the case of carbon nanomaterials. In this paper we show that by combining advanced computational techniques augmented by machine learning methods with x-ray absorption spectroscopy (XAS) and electrochemical measurements, it is possible to obtain a deeper understanding of the correlation between local surface chemistry and electrochemical performance. As a test case we show how by computationally assessing the growth of amorphous carbon (a-C) thin films at the atomic level, we can create computational structural motifs that may in turn be used to deconvolute the XAS data from the real samples resulting in local chemical information. Then, by carrying out electrochemical measurements on the same samples from which x-ray spectra were measured and that were further characterized computationally, it is possible to gain insight into the interplay between the local surface chemistry and electrochemical performance. To demonstrate this methodology, we proceed as follows: after assessing the basic electrochemical properties of a-C films, we investigate the effect of short HNO3 treatment on the sensitivity of these electrodes towards an inner sphere redox probe dopamine to gain knowledge about the influence of altered surface chemistry to observed electrochemical performance. These results pave the way towards a more general assessment of electrocatalysis in different systems and provide the first steps towards data driven tailoring of electrode surfaces to gain optimal performance in a given application

Structure-property relationships in carbon electrochemistry

Abstract Carbonaceous nanomaterials can be a game changing materials in many technological fields, especially in electroanalytical applications. However, there is no consensus on the associations between the structure and electrochemical performance of these nanomaterials — even for the most basic electrochemical properties. This challenge stems from the fact that typically carbonaceous nanomaterials are obtained from various sources and not characterized properly. Therefore, to solve this deadlock we carry out systematic electrochemical characterization for a set of in-house fabricated as well as physicochemically thoroughly characterized carbon nanomaterials. We will then proceed to establish structure — performance associations for these materials. In addition, we will highlight how sensitive the electrochemical performance of these materials can be to small changes in their structural properties. Further, we emphasize the lack of correlation between electrochemical performance of electrode materials as determined using outer sphere redox (OSR) and inner sphere redox (ISR) probes the latter being highly analyte specific. As a first consistent set of electrochemical data obtained by using well characterized carbonaceous nanomaterials, this work will provide solid basis to expand the use of these materials in more complex electroanalytical as well as other applications

Effect of electrochemical oxidation on physicochemical properties of Fe‐containing single‐walled carbon nanotubes

Abstract Metal catalysts are necessary for fabricating carbon nanotubes, but are often considered impurities in the end products, and arduous steps are used to remove catalyst residues from the nanotube structure. However, as metals can be electrocatalytic, instead of removing them we can utilize their role in detection of analgesics. Herein, we study the physicochemical properties of Fe‐containing single‐walled carbon nanotubes (SWCNTs), and the effect of simple oxidative pretreatment on them. We show that a gentle anodic pretreatment i) increased the amount of oxidized Fe nanoparticles, most likely exhibiting phases Fe₃O₄ and Fe₂O₃ and ii) effectively removed disordered carbonaceous material from SWCNT bundles surfaces. Pretreatment had only a marginal effect on sensitivity towards analgesics. However, interestingly, selectivity of Fe‐SWCNTs towards paracetamol and morphine could be modified with pretreatment. Through this kind of in‐depth investigation, we can, to a certain extent, correlate various material properties of SWCNTs with the observed electrochemical performance. This approach allows us to evaluate what factors in SWCNTs truly affect the electrochemical detection of biomolecules

Geometrical and chemical effects on the electrochemistry of single-wall carbon nanotube (SWCNT) network electrodes

Abstract Single-wall carbon nanotube (SWCNT) network is a promising electrode material for bio detection. Unfortunately, the associations between their physical as well as chemical properties and observed electrochemical performance are not known. This hinders any systematic optimization of the network properties towards specific analytes. Here we present a consistent physicochemical and electrochemical characterization of differently treated SWCNT networks. The results unambiguously show that (i) even if the electrochemical properties of different electrodes are practically identical when assessed by surface insensitive outer sphere redox (OSR) probes their behavior with inner sphere redox (ISR) probes can be drastically different. Further, (ii) the choice of the modification method (structural, chemical, electrochemical) heavily depends on nature of the target analyte, which are typically ISR probes. Although, (iii) chemical changes in the carbon phase appeared to be minor, effects of different treatments on oxidation states of Fe appeared to have a strong effect on the electrochemical performance of the networks in the case of ISR probes

X-ray spectroscopy fingerprints of pristine and functionalized graphene

Abstract In this work, we demonstrate how to identify and characterize the atomic structure of pristine and functionalized graphene materials from a combination of computational simulation of X-ray spectra, on the one hand, and computer-aided interpretation of experimental spectra, on the other. Despite the enormous scientific and industrial interest, the precise structure of these 2D materials remains under debate. As we show in this study, a wide range of model structures from pristine to heavily oxidized graphene can be studied and understood with the same approach. We move systematically from pristine to highly oxidized and defective computational models, and we compare the simulation results with experimental data. Comparison with experiments is valuable also the other way around; this method allows us to verify that the simulated models are close to the real samples, which in turn makes simulated structures amenable to several computational experiments. Our results provide ab initio semiquantitative information and a new platform for extended insight into the structure and chemical composition of graphene-based materials

Unmodified and multi-walled carbon nanotube modified tetrahedral amorphous carbon (ta-C) films as in vivo sensor materials for sensitive and selective detection of dopamine

Abstract Unmodified and multi-walled carbon nanotube (MWCNT) modified tetrahedral amorphous carbon (ta-C) films of 15 and 50 nm were investigated as potential in vivo sensor materials for the detection of dopamine (DA) in the presence of the main interferents, ascorbic acid (AA) and uric acid (UA). The MWCNTs were grown directly on ta-C by chemical vapor deposition (designated as ta-C+CNT) and were characterized with X-ray photoelectron spectroscopy, Raman spectroscopy, scanning and transmission electron microscopy. Electroanalytical sensitivity and selectivity were determined with cyclic voltammetry. Biocompatibility of the materials was assessed with cell cultures of mouse neural stem cells (mNSCs). The detection limits of DA for both ta-C and ta-C+CNT electrodes ranged from 40 to 85 nM, which are well within the required range for in vivo detection. The detection limits were lower for both ta-C and ta-C+CNT electrodes with 50 nm of ta-C compared to 15 nm. The ta-C electrodes showed a large dynamic linear range of 0.01–100 µM but could not resolve between the oxidation peaks of DA, AA and UA. Modification with MWCNTs, however, resulted in excellent selectivity and all three analytes could be detected simultaneously at physiologically relevant concentrations using cyclic voltammetry. Based on cell culture of mNSCs, both ta-C and ta-C+CNT exhibited good biocompatibility, demonstrating their potential as in vivo sensor materials for the detection of DA

Introduction of an electrochemical point-of-care assay for quantitative determination of paracetamol in finger-prick capillary whole blood samples

AimsMeasuring venous plasma paracetamol concentrations is time- and resource-consuming. We aimed to validate a novel electrochemical point-of-care (POC) assay for rapid paracetamol concentration determinations. MethodsTwelve healthy volunteers received 1 g oral paracetamol, and its concentrations were analysed 10 times over 12 h for capillary whole blood (POC), venous plasma (high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS)), and dried capillary blood (HPLC-MS/MS). ResultsAt concentrations >30 mu M, POC showed upward biases of 20% (95% limits of agreement [LOA] -22 to 62) and 7% (95% LOA -23 to 38) compared with venous plasma and capillary blood HPLC-MS/MS, respectively. There were no significant differences between mean concentrations for the paracetamol elimination phase. ConclusionsUpward biases in POC compared with venous plasma HPLC-MS/MS were likely due to higher paracetamol concentrations in capillary blood than in venous plasma and to faulty individual sensors. The novel POC method is a promising tool for paracetamol concentration analysis.Peer reviewe

Biofouling affects the redox kinetics of outer and inner sphere probes on carbon surfaces drastically differently

Abstract Biofouling imposes a significant threat for sensing probes used in vivo. Antifouling strategies commonly utilize a protective layer on top of the electrode but this may compromise performance of the electrode. Here, we investigated the effect of surface topography and chemistry on fouling without additional protective layers. We have utilized two different carbon materials; tetrahedral amorphous carbon (ta-C) and SU-8 based pyrolytic carbon (PyC) in their typical smooth thin film structure as well as with a nanopillar topography templated from black silicon. The near edge X-ray absorption fine structure (NEXAFS) spectrum revealed striking differences in chemical functionalities of the surfaces. PyC contained equal amounts of ketone, hydroxyl and ether/epoxide groups, while ta-C contained significant amounts of carbonyl groups. Overall, oxygen functionalities were significantly increased on nanograss surfaces compared to the flat counterparts. Neither bovine serum albumin (BSA) or fetal bovine serum (FBS) fouling caused major effects on electron transfer kinetics of outer sphere redox (OSR) probe Ru(NH3)63+ on any of the materials. In contrast, negatively charged OSR probe IrCl62− kinetics were clearly affected by fouling, possibly due to the electrostatic repulsion between redox species and the anionically-charged proteins adsorbed on the electrode and/or stronger interaction of the proteins and positively charged surface. The OSR probe kinetics were less affected by fouling on PyC, probably due to conformational changes of proteins on the surface. Dopamine (DA) was tested as an inner sphere redox (ISR) probe and as expected, the kinetics were heavily dependent on the material; PyC had very fast electron transfer kinetics, while ta-C had sluggish kinetics. DA electron transfer kinetics were heavily affected on all surfaces by fouling (ΔEp increase 30—451%). The effect was stronger on PyC, possibly due to the more strongly adhered protein layer limiting the access of the probe to the inner sphere