Potential applications of negative tone development in advanced lithography

Advanced lithography requires resolution enhancement techniques (customized illumination mode, litho friendly design), and alternative process flow schemes (double exposure, double patterning) in order to meet the requirements of the ITRS technology roadmap and to extend the applications of a full-field scanner with a 1.35 numerical aperture (NA) that represents the physical limit of water-based immersion ArF lithography.Today, one of the most interesting alternative processes uses the patterning inversion through a negative tone development (NTD) process step. Traditionally, the patterning (contacts or trenches) is done by using a dark field mask in combination with positive tone resist and positive tone development (PTD). By using a solvent-based developer (NTD) and a bright field mask, the same features can be transferred into a positive resist with the benefit of better image contrast and, consequently, better line width roughness (LWR) and resolution.In this work we have explored the potential applications of NTD for trenches and contact holes for the 45 nm technology node requirements and beyond. The NTD process is a promising option considering the impact on process window, LWR, CD uniformity and defectivity. The experimental result of this alternative approach to print critical dark field levels in an advanced lithography boundary has been explored.     

Bioinspired Tunable Lens with Muscle‐Like Electroactive Elastomers

Optical lenses with tunable focus are needed in several fields of application, such as consumer electronics, medical diagnostics and optical communications. To address this need, lenses made of smart materials able to respond to mechanical, magnetic, optical, thermal, chemical, electrical or electrochemical stimuli are intensively studied. Here, we report on an electrically tunable lens made of dielectric elastomers, an emerging class of “artificial muscle” materials for actuation. The optical device is inspired by the architecture of the crystalline lens and ciliary muscle of the human eye. It consists of a fluid‐filled elastomeric lens integrated with an annular elastomeric actuator working as an artificial muscle. Upon electrical activation, the artificial muscle deforms the lens, so that a relative variation of focal length comparable to that of the human lens is demonstrated. The device combined optical performance with compact size, low weight, fast and silent operation, shock tolerance, no overheating, low power consumption, and possibility of implementation with inexpensive off‐the‐shelf elastomers. Results show that combing bioinspired design with the unique properties of dielectric elastomers as artificial muscle transducers has the potential to open new perspectives on tunable optics.     

Chaos in symmetric phase oscillator networks

Phase-coupled oscillators serve as paradigmatic models of networks of weakly interacting oscillatory units in physics and biology. The order parameter which quantifies synchronization so far has been found to be chaotic only in systems with inhomogeneities. Here we show that even symmetric systems of identical oscillators may not only exhibit chaotic dynamics, but also chaotically fluctuating order parameters. Our findings imply that neither inhomogeneities nor amplitude variations are necessary to obtain chaos; i.e., nonlinear interactions of phases give rise to the necessary instabilities.     

Internal quality control as a tool for planning a robustness study regarding a multiresidue method for pesticides found in olive oil

The implementation of the internal quality assurance program allows for demonstration of the performance characteristics of a method, as well as the avoidance of erroneous results. There is increasing concern in testing laboratories to ensure that the analytical process remains stable, giving reliable results under statistical control. Robustness is tested by introducing variations in experimental conditions and examining the effects on the results. The European document SANCO/12495/2011, “Method validation and quality control procedures for pesticide residue analysis in food and feed”, defines robustness as a parameter that can be derived from ongoing method verification. Internal quality control tools, such as the recovery control chart, were employed in this study to enhance the stability of the recovery rates and to investigate the experimental conditions that have a major influence on the quantification of recovery rates. The method investigated in this study permitted us to investigate eighteen pesticides in olive oil by using a gas chromatography–mass spectrometry technique. This method has been accredited to ISO/IEC 17025:2005 standards and was applied for 1 year in routine conditions for pesticide residues at the Italian National Reference Laboratory. The recovery control chart has showed that all recovery rates for 1 year were close to the maximum limit (120 %) of recovery performance criteria. Consequently, a “positive” bias has affected all data over longer periods of time. A robustness test was planned in order to investigate the grounds that most influenced the variability of the results. The robustness test involved the following three parameters: solvent used to dissolve the final extract, internal standards, and type of olive oil.     

Solid‐phase microextraction with fast GC combined with a high‐speed triple quadrupole mass spectrometer for targeted and untargeted food analysis

The present contribution is focused on the evaluation of a high‐speed triple quadrupole mass spectrometer, carried out under moderately fast GC conditions (analysis time: 16.6 min). The mass spectrometric instrument can be operated under high‐speed GC conditions, in both full‐scan (maximum scan speed: 20 000 amu/s) and multiple reaction monitoring (MRM) modes (minimum dwell time: 0.01 s). Additionally, the mass spectrometric system can generate full scan and MRM information, simultaneously and rapidly. A headspace solid‐phase microextraction with fast GC coupled to triple quadrupole MS approach was developed for the: (i) qualitative untargeted analysis of brewed tea volatiles, and (ii) MRM qualitative and quantitative analysis of targeted volatiles (also in brewed tea), namely 30 phytosanitary contaminants. The performance of the triple quadrupole instrument was satisfactory both for identification and quantification purposes. Furthermore, the method sensitivity was more than sufficient for the requirements of current legislation. Method validation, related to the MRM analysis, was performed considering: precision of quantification data (maximum coefficient of variation value: 12.0%) and quantification/qualification ion ratios (maximum coefficient of variation value: 14.4%), along with limits of detection (4 parts per trillion–5 parts per billion range) and quantification (14 parts per trillion–16 parts per billion range).     

Structural analysis of protein complexes with sodium alkyl sulfates by small-angle scattering and polyacrylamide gel electrophoresis

Small-angle X-ray (SAXS) and neutron (SANS) scattering is used to probe the structure of protein-surfactant complexes in solution and to correlate this information with their performance in gel electrophoresis. Proteins with sizes between 6.5 to 116 kDa are denatured with sodium alkyl sulfates (SC(x)S) of variable tail lengths. Several combinations of proteins and surfactants are analyzed to measure micelle radii, the distance between micelles, the extension of the complex, the radius of gyration, and the electrophoretic mobility. The structural characterization shows that most protein-surfactant complexes can be accurately described as pearl-necklace structures with spherical micelles. However, protein complexes with short surfactants (SC(8)S) bind with micelles that deviate significantly from spherical shape. Sodium decyl (SC(10)S) and dodecyl (SC(12)S, more commonly abbreviated as SDS) sulfates result in the best protein separations in standard gel electrophoresis. Particularly, SC(10)S shows higher resolutions for complexes of low molecular weight. The systematic characterization of alkyl sulfate surfactants demonstrates that changes in the chain architecture can significantly affect electrophoretic migration so that protein-surfactant structures could be optimized for high resolution protein separations.     

An XPS investigation on glucose oxidase and Ni/Al hydrotalcite interaction

In this work, a Ni/Al hydrotalcite (HT) was used as glucose oxidase (GOx) immobilizer. Small‐area and angle‐resolved X‐ray photoelectron spectra were recorded on HTs electrosynthesized on Pt in the absence and in the presence of GOx, and compared with those obtained for a Pt surface, modified with the electrosynthesized HT, on which a drop of GOx solution was deposited. The simultaneous electrodeposition of HT + GOx resulted in a compact deposit, thicker than the XPS sampling depth (>10 nm), that is not homogeneous in the lateral and in‐depth composition. The presence of GOx can be deduced comparing the N1s spectra of HT and HT + GOx: in the latter, the N1s component at 400 eV binding energy (BE) is predominant whilst, depending on the analyzed point, a small or no contribution from the component at 407.2 eV, due to nitrate, is revealed. Angle‐resolved XPS provides evidence on the in‐depth composition of anions, cations and GOx. The results highlight the crucial role played by nickel in GOx immobilization. On the basis of the results, it can be suggested that enzyme activity is unevenly distributed and is localized in small areas, where Ni concentration is higher. Copyright © 2010 John Wiley & Sons, Ltd.     

Fluorescence of commercial Pluronic F127 samples: Temperature-dependent micellization

We present a novel approach of using the butylated hydroxytoluene (BHT) antioxidant found in commercial Pluronic F127 samples as a marker of polymer aggregation. The BHT marker was compared to the pyrene dye and static light scattering methods as a way to measure the critical micelle concentration (CMC) and critical micelle temperature (CMT). The n→π(?) transitions of BHT are sensitive to the microenvironment as demonstrated by plotting the fractional intensities of its excitation (≈280nm) and emission (≈325nm) peaks. BHT is more sensitive to changes in temperature than concentration. The partition coefficient increases ≈40-fold for pyrene compared to ≈2-fold for BHT when the temperature is increased from 25 to 37°C. CMT values determined using the BHT fluorescence decrease with increasing F127 concentration. Our results show that BHT can be used as a reliable marker of changes in the microenvironment of Pluronic F127.     

Application of circular dichroism spectroscopy in the study of mixed-valence asymmetric ruthenium polypyridyl complexes

Circular dichroism (CD) spectroelectrochemistry is used to determine the extent of singly occupied molecular orbital delocalization in mixed-valence multinuclear complexes, specifically the mixed-valence Ru(II)Ru(III) states of the four diastereoisomers of [(Ru(bpy)(2))(2)(bpt)](3+) [1; bpy = 2,2'-bipyridyl and bpt = 3,5-bis(pyrid-2'-yl)-1,2,4-triazolato anion]. The complex was found to be stable to thermal racemization in the three oxidation states, but photoracemization in the Ru(II)Ru(II) state was observed.     

Multivariate Multiscale Cosine Similarity Entropy and Its Application to Examine Circularity Properties in Division Algebras

The extension of sample entropy methodologies to multivariate signals has received considerable attention, with traditional univariate entropy methods, such as sample entropy (SampEn) and fuzzy entropy (FuzzyEn), introduced to measure the complexity of chaotic systems in terms of irregularity and randomness. The corresponding multivariate methods, multivariate multiscale sample entropy (MMSE) and multivariate multiscale fuzzy entropy (MMFE), were developed to explore the structural richness within signals at high scales. However, the requirement of high scale limits the selection of embedding dimension and thus, the performance is unavoidably restricted by the trade-off between the data size and the required high scale. More importantly, the scale of interest in different situations is varying, yet little is known about the optimal setting of the scale range in MMSE and MMFE. To this end, we extend the univariate cosine similarity entropy (CSE) method to the multivariate case, and show that the resulting multivariate multiscale cosine similarity entropy (MMCSE) is capable of quantifying structural complexity through the degree of self-correlation within signals. The proposed approach relaxes the prohibitive constraints between the embedding dimension and data length, and aims to quantify the structural complexity based on the degree of self-correlation at low scales. The proposed MMCSE is applied to the examination of the complex and quaternion circularity properties of signals with varying correlation behaviors, and simulations show the MMCSE outperforming the standard methods, MMSE and MMFE.