Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Attacks on Block Ciphers of Low Algebraic Degree

In this paper an attack on block ciphers is introduced, the interpolation attack. This method is useful for attacking ciphers that use simple algebraic functions (in particular quadratic functions) as S-boxes. Also, attacks based on higher-order differentials are introduced. They are special and important cases of the interpolation attacks. The attacks are applied to several block ciphers, the six-round prototype cipher by Nyberg and Knudsen, which is provably secure against ordinary differential cryptanalysis, a modified version of the block cipher SHARK, and a block cipher suggested by Kiefer. Received April 1999 and revised October 2000 Online publication 9 April 2001     

Electrical and stability properties and ultrasonic microscope characterisation of low temperature co-fired ceramics resistors

This paper presents systematic investigations of electrical and stability properties of various low temperature co-fired ceramics (LTCC) resistors. One of the goals of this work was to check the compatibility of LTCC materials (tapes, resistive and conductive inks) from various manufacturers. Three commercially available green tapes and three LTCC resistor/conductor systems were examined. The resistive inks with 1 kΩ/sq. nominal sheet resistance were used. Buried (inside) and surface resistors were laminated and fired according to the tape manufacturers’ recommendations. The influence of dimensional effect on sheet resistance and hot temperature coefficient of resistance, the temperature dependence of resistance in a wide temperature range (from −180°C to +130°C), long-term stability of thermally aged as-fired resistors (150°C, 500 h) and durability to high-voltage micro- or nanosecond pulses (50 ns pulses with 4000 V/mm maximum electric field or 10 μs ones with 700–1000 V/mm electrical field) were carried out for electrical and stability characterisation of LTCC resistors. Non-destructive scanning acoustic microscope diagnostics was applied for structure investigation and estimation of lamination and cofiring process quality of buried LTCC resistors.     

Photovoltaic Devices: Highly Conductive PEDOT:PSS Electrode with Optimized Solvent and Thermal Post‐Treatment for ITO‐Free Organic Solar Cells (Adv. Funct. Mater. 6/2011)

Highly conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as stand‐alone electrodes for organic solar cells have been optimized using a solvent post‐treatment method. The treated PEDOT:PSS films show enhanced conductivities up to 1418 S cm^?1, accompanied by structural and chemical changes. The effect of the solvent treatment on PEDOT:PSS has been investigated in detail and is shown to cause a reduction of insulating PSS in the conductive polymer layer. Using these optimized electrodes, ITO‐free, small molecule organic solar cells with a zinc phthalocyanine (ZnPc):fullerene C₆₀ bulk heterojunction have been produced on glass and PET substrates. The system was further improved by pre‐heating the PEDOT:PSS electrodes, which enhanced the power conversion efficiency to the values obtained for solar cells on ITO electrodes. The results show that optimized PEDOT:PSS with solvent and thermal post‐treatment can be a very promising electrode material for highly efficient flexible ITO‐free organic solar cells.     

Detection of skin cancer by classification of Raman spectra

Skin lesion classification based on in vitro Raman spectroscopy is approached using a nonlinear neural network classifier. The classification framework is probabilistic and highly automated. The framework includes a feature extraction for Raman spectra and a fully adaptive and robust feedforward neural network classifier. Moreover, classification rules learned by the neural network may be extracted and evaluated for reproducibility, making it possible to explain the class assignment. The classification performance for the present data set, involving 222 cases and five lesion types, was 80.5%+/-5.3% correct classification of malignant melanoma, which is similar to that of trained dermatologists based on visual inspection. The skin cancer basal cell carcinoma has a classification rate of 95.8%+/-2.7%, which is excellent. The overall classification rate of skin lesions is 94.8%+/-3.0%. Spectral regions, which are important for network classification, are demonstrated to reproduce. Small distinctive bands in the spectrum, corresponding to specific lipids and proteins, are shown to hold the discriminating information which the network uses to diagnose skin lesions.     

Transparent,Stimuli‐Responsive Films from Cellulose‐Based Organogel Nanoparticles

The use of bio‐based nanoscaled cellulose for the construction of novel functional materials has progressed rapidly over the past years. In comparison to most of studies starting with the hydrophilic nanoscaled cellulose, surface‐stearoylated cellulose nanoparticles (SS‐CNPs) are used in this report for the construction of multifunctional, responsive films. SS‐CNPs with an average size of 115 ± 0.5 nm are obtained after the surface‐modification of cellulose under heterogeneous conditions. Crystalline cellulose core is present within SS‐CNPs according to solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. SS‐CNPs show excellent dispersibility in nonpolar solvents and form temperature‐responsive organogels in tetrahydrofuran (THF) at low temperature or after long time storage at room temperature. Moreover, transparent and self‐standing films of SS‐CNPs from their THF‐suspension show solvent‐responsive surface wettability and responsive shape‐memory property. SS‐CNPs can also be used for the fabrication of nanocomposite films together with nonpolar compounds, such as (2‐stearoylaminoethyl) rhodamine B. Thus, these novel SS‐CNPs derived from sustainable cellulose fibers are promising candidates for the construction of novel functional materials.     

On the Relation between Morphology and FET Mobility of Poly(3‐alkylthiophene)s at the Polymer/SiO2 and Polymer/Air Interface

The influence of the interface of the dielectric SiO₂ on the performance of bottom‐contact, bottom‐gate poly(3‐alkylthiophene) (P3AT) field‐effect transistors (FETs) is investigated. In particular, the operation of transistors where the active polythiophene layer is directly spin‐coated from chlorobenzene (CB) onto the bare SiO₂ dielectric is compared to those where the active layer is first spin‐coated then laminated via a wet transfer process such that the film/air interface of this film contacts the SiO₂ surface. While an apparent alkyl side‐chain length dependent mobility is observed for films directly spin‐coated onto the SiO₂ dielectric (with mobilities of ≈10^?3 cm² V^?1 s^?1 or less) for laminated films mobilities of 0.14 ± 0.03 cm² V^?1 s^?1 independent of alkyl chain length are recorded. Surface‐sensitive near edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements indicate a strong out‐of‐plane orientation of the polymer backbone at the original air/film interface while much lower average tilt angles of the polymer backbone are observed at the SiO₂/film interface. A comparison with NEXAFS on crystalline P3AT nanofibers, as well as molecular mechanics and electronic structure calculations on ideal P3AT crystals suggest a close to crystalline polymer organization at the P3AT/air interface of films from CB. These results emphasize the negative influence of wrongly oriented polymer on charge carrier mobility and highlight the potential of the polymer/air interface in achieving excellent “out‐of‐plane” orientation and high FET mobilities.     

Regularized Pre-image Estimation for Kernel PCA De-noising

The main challenge in de-noising by kernel Principal Component Analysis (PCA) is the mapping of de-noised feature space points back into input space, also referred to as “the pre-image problem”. Since the feature space mapping is typically not bijective, pre-image estimation is inherently illposed. As a consequence the most widely used estimation schemes lack stability. A common way to stabilize such estimates is by augmenting the cost function by a suitable constraint on the solution values. For de-noising applications we here propose Tikhonov input space distance regularization as a stabilizer for pre-image estimation, or sparse reconstruction by Lasso regularization in cases where the main objective is to improve the visual simplicity. We perform extensive experiments on the USPS digit modeling problem to evaluate the stability of three widely used pre-image estimators. We show that the previous methods lack stability in the is non-linear regime, however, by applying our proposed input space distance regularizer the estimates are stabilized with a limited sacrifice in terms of de-noising efficiency. Furthermore, we show how sparse reconstruction can lead to improved visual quality of the estimated pre-image.