Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Self‐formed Schottky barrier induced selector‐less RRAM for cross‐point memory applications

We propose a selector‐less Pr_0.7Ca_0.3MnO₃ (PCMO) based resistive‐switching RAM (RRAM) for high‐density cross‐point memory array applications. First, we investigate the inhomogeneous barrier with an effective barrier height (Φ_eff), i.e., self‐formed Schottky barrier. In addition, a scalable 4F² selector‐less cross‐point 1 kb RRAM array has been successfully fabricated, demonstrating set, reset, and read operation for high cell efficiency and high‐density memory applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Binary phase shaping for selective single‐beam CARS spectroscopy and imaging of gas‐phase molecules

We report on mode‐selective single‐beam coherent anti‐Stokes Raman scattering spectroscopy of gas‐phase molecules. Binary phase shaping (BPS) is used to produce single‐mode excitation of O₂, N₂, and CO₂ vibrational modes in ambient air and gas‐phase mixtures, with high‐contrast rejection of off‐resonant Raman modes and efficient nonresonant‐background suppression. In particular, we demonstrate independent excitation of CO₂ Fermi dyads at ∼1280 and ∼1380 cm⁻¹ and apply BPS for high‐contrast imaging of CO₂ jet in ambient air. Copyright © 2010 John Wiley & Sons, Ltd.     

Silver macro‐texture substrates fabricated by plasma selective etching for surface‐enhanced Raman scattering

We have demonstrated a novel method to generate the nanostructured substrate that shows a large enhancement with a spatially uniform enhancement factor of approximately 10⁶ in surface enhanced Raman scattering (SERS). The substrates are fabricated using plasma selective etching. First, the Al₂O₃–TiC template which contains mixed Al₂O₃ and TiC grains with the diameters of ~400 nm is selected as a base plate. The Al₂O₃ and TiC grains have different physical properties, such as hardness, which corresponds to different etching rate in a plasma gas. Then, the Al₂O₃–TiC substrate is selectively etched to generate a random macro‐texture (MT) with different depths using the plasma of mixed gas of Ar and C₂H₄. Third, the MT substrate is deposited with a silver film (Ag). We further demonstrate that by varying the thickness of Ag layer, the EF is different which is confirmed by the plasmonic localized electric fields calculations using finite difference time domain. Finally, we combine this novel Ag MT substrate with ultrathin dielectric film, and the prepared substrates are coated with a 10 Å ta‐C film. The 10 Å ta‐C film can protect the oxygen‐free Ag in air and prevent Ag ionizing in aqueous solutions. More importantly, the ultrathin ta‐C can release the strongest plasmonic electric field to the outside of ta‐C layer and get a higher electric field than the uncoated Ag substrate. We expect that this method has more potential applications in analytic assays using SERS technology. Copyright © 2012 John Wiley & Sons, Ltd.     

Determination of N and O‐atoms and N2 (A) Metastable Molecule Densities in the Afterglows of N2‐H2, Ar‐N2‐H2 and Ar‐N2‐O2 Microwave Discharges

Early afterglows of N₂‐H₂, Ar‐N₂‐H₂ and Ar‐N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atoms and the N₂ (A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N and O‐atoms and measurements of NO and N₂ band intensities. If an uncertainty of 30% is estimated on N‐atomic density, an inaccuracy of one order of magnitude is obtained on the O and N₂ (A) densities. In N₂‐(0.05‐2.5%)H₂ and Ar‐(1‐50%)N₂‐(0.05‐2.5%) H₂ gas mixtures, the O‐atoms are coming from O₂ impurities in the discharge. Concentrations of N and O‐atoms and of N₂ (A) densities are compared to the ones obtained in Ar‐(5‐50%)N₂‐(0.2‐2.5%) O₂ gas mixtures in which a controlled amount of O₂ is added. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First‐principles study on the concentrations of native point defects in high‐dielectric‐constant binary oxide materials

The intrinsic concentrations of point defects in high‐k binary oxide materials of HfO₂, ZrO₂, Y₂O₃ and La₂O₃ are evaluated on the basis of first‐principles calculations. Oxygen defects are found to dominate over a wide range of the oxygen chemical potential. Neutral oxygen vacancies are likely to be responsible for electron trapping in the investigated materials. In HfO₂ and ZrO₂, oxygen Frenkel pairs are likely to form. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reduction of low‐frequency noise in multilayer MoS2 FETs using a Fermi‐level depinning layer

Two‐dimensional transition metal dichalcogenides (TMDCs) are potential candidate materials for future thin‐film field effect transistors (FETs). However, many aspects of this device must be optimized for practical applications. In addition, low‐frequency noise that limits the design window of electronic devices, in general, must be minimized for TMD‐based FETs. In this study, the low‐frequency noise characteristics of multilayer molybdenum disulphide (MoS₂) FETs were investigated in detail, with two different contact structures: titanium (Ti) metal–MoS₂ channel and Ti metal–TiO₂ interlayer–MoS₂ channel. The results showed that the noise level of the device with a TiO₂ interlayer reduced by one order of magnitude compared with the device without the TiO₂ interlayer. This substantial improvement in the noise characteristics could be explained using the carrier number of fluctuation model. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Deep levels in low‐energy electron‐irradiated 4H‐SiC

Deep levels introduced by low‐energy (200 keV) electron irradiation in n‐type 4H‐SiC epitaxial layers grown by chemical vapour deposition were studied by deep level transient spectroscopy (DLTS) and photoexcitation electron paramagnetic resonance (photo‐EPR). After irradiation, several DLTS levels, EH1, EH3, Z_1/2, EH5 and EH6/7, often reported in irradiated 4H‐SiC, were observed. In irradiated freestanding films from the same wafer, the EPR signals of the carbon vacancy in the positive and negative charge states, V_C⁺ and V_C^‐, respectively, can be observed simultaneously under illumination with light of certain photon energies. Comparing the ionization energies obtained from DLTS and photo‐EPR, we suggest that the EH6/7 (at ～E_C – 1.6 eV) and EH5 (at ～E_C – 1.0 eV) electron traps may be related to the single donor (+ | 0) and the double acceptor (1– | 2–) level of V_C, respectively. Judging from the relative intensity of the DLTS signals, the EH6/7 level may also be contributed to by other unidentified defects. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In‐situ X‐ray diffraction of mechanically milled β‐Al3Mg2 powders

The structure evolution during heating of mechanically milled single‐phase β‐Al₃Mg₂ has been investigated by in‐situ X‐ray diffraction. The nanoscale supersaturated Al(Mg) solid solution formed during milling transforms back to the original β‐Al₃Mg₂ phase through a sequence of phase transformations. At low temperatures, an increasing amount of Mg is rejected from the solid solution with increasing temperature. At intermediate temperatures, the β′‐phase, a hexagonal phase with approximate composition Al₃Mg₂, forms. Finally, at higher temperatures the original β‐Al₃Mg₂ phase is restored, indicating that the formation of the supersaturated solid solution during milling can be reversed by appropriate heat treatment. The phase transformations during heating are gradual and the temperature ranges of stability of the different structure configurations are quite large, all exceeding 50 K. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical studies on 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) and its derivatives

In this work, a set of derivatives of 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) with different energetic substituents (?N₃, –NO₂, –NH₂, –NF₂) have been studied at the Becke, three‐parameter, Lee–Yang–Parr/aug‐cc‐pvdz, Becke, three‐parameter, Lee–Yang–Parr/6‐31G(d), Becke, three‐parameter, Perdew 86/6‐31G(d), and Becke three‐parameter, Perdew–Wang 91/6‐31G(d,p) levels of density functional theory. The gas‐phase heats of formation were predicted with isodesmic reactions and the condensed‐phase HOFs were estimated with the Politzer approach. The effects of different functionals and basis sets were analyzed. –N₃ and –NO₂ greatly increase while –NH₂ and –NF₂ slightly decrease heats of formation. An analysis of the bond dissociation energies and impact sensitivity shows that all compounds have good stability. The crystal densities (1.82–2.00 g/cm³) computed from molecular packing calculations are big for all compounds and that of the –NF₂ derivative is the largest. All derivatives have higher detonation velocity and detonation pressure than PRAN. Compounds 3 and 4 (R = NO₂ and NF₂) have better performance than hexahydro‐1,3,5‐trinitro‐1,3,5‐trizine and the performance of 4 is quite close to that of 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane, they are promising candidates of high energy compounds and worth further investigations. Copyright © 2012 John Wiley & Sons, Ltd.     

21.0%‐efficient co‐diffused screen printed n‐type silicon solar cell with rear‐side boron emitter

Plasma enhanced chemical vapor deposition (PECVD) is applied to deposit boron silicate glasses (BSG) acting as boron diffusion source during the fabrication of n‐type silicon solar cells. We characterize the resulting boron‐diffused emitter after boron drive‐in from PECVD BSG by measuring the sheet resistances R_sheet,B and saturation current densities J_0,B. For process optimization, we vary the PECVD deposition parameters such as the gas flows of the precursor gases silane and diborane and the PECVD BSG layer thickness. We find an optimum gas flow ratio of SiH₄/B₂H₆= 8% and layer thickness of 40 nm. After boron drive in from these PECVD BSG diffusion sources, a low J_0,B values of 21 fA/cm² is reached for R_sheet,B = 70 Ω/□. The optimized PECVD BSG layers together with a co‐diffusion process are implemented into the fabrication process of passivated emitter and rear totally diffused (PERT) back junction (BJ) cells on n‐type silicon. An independently confirmed energy conversion efficiency of 21.0% is achieved on 15.6 × 15.6 cm² cell area with a simplified process flow. This is the highest efficiency reported for a co‐diffused n‐type PERT BJ cell using PECVD BSG as diffusion source. A loss analysis shows a small contribution of 0.13 mW/cm² of the boron diffusion to the recombination loss proving the high quality of this diffusion source. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Spin–orbit stiffness of the spin‐polarized electron gas

In a spin‐polarized electron gas, Coulomb interaction couples the spin and motion degrees of freedom to build propagating spin waves. The spin wave stiffness S_sw quantifies the energy cost to trigger such excitation by perturbing the kinetic energy of the electron gas (i.e. putting it in motion). Here we introduce the concept of spin–orbit stiffness, S_so, as the energy necessary to excite a spin wave with a spin polarization induced by spin–orbit coupling. This quantity governs the Coulombic enhancement of the spin–orbit field acting of the spin wave. First‐principles calculations and electronic Raman scattering experiments carried out on a model spin‐polarized electron gas, embedded in a CdMnTe quantum well, demonstrate that S_so = S_sw. Through optical gating of the structure, we demonstrate the reproducible tuning of S_so by a factor of 3, highlighting the great potential of spin–orbit control of spin waves in view of spintronics applications. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

THz radiation generation via the interaction of two‐colour ultra‐short laser pulses with SO2 and NH3 gases

In this work, using a two‐dimensional particle‐in‐cell Monte Carlo collision computation method, terahertz (THz) radiation generation via the interaction of two‐colour, ultra‐short, high‐power laser pulses with the polyatomic molecular gases sulphur dioxide (SO₂) and ammonia (NH₃) is examined. The influence of SO₂ and NH₃ pressures and two‐colour laser pulse parameters, i.e., pulse shape, pulse duration, and beam waist, on the THz radiation generation is studied. It is shown that the THz signal generation from SO₂ and NH₃ increases with the background gas pressure. It is seen that the THz emission intensity for both gases at higher laser pulse durations is higher. Moreover, for these polyatomic gases, the plasma current density increases with increase in the laser pulse beam waist. A more powerful THz radiation intensity with a larger time to peak of the plasma current density is observed for SO₂ compared to NH₃. In addition, many THz signals with small intensities are observed for both polyatomic gases. It is seen that for both SO₂ and NH₃ the generated THz spectral intensity is higher at higher gas pressures.     

Micro‐Raman and photoluminescence analysis of composite vanadium oxide/poly‐vinyl acetate fibres synthesised by electro‐spinning

Composite vanadium oxide (VO_x)‐based fibres were synthesised by the electro‐spinning method combined with conventional sol–gel processing using polyvinyl acetate (PVAc) as a polymeric binder and vanadium oxytriisopropoxide as a vanadium oxide precursor. The microstructure and composition of as‐spun and calcined (300–500 °C) VO_x–PVAc fibres were systematically investigated by scanning electron microscopy, thermogravimetry, reflectance infrared Fourier transform, micro‐Raman spectroscopy and photoluminescence in view of their possible use in gas sensor fabrication. The comparative discussion of the characterization results indicates that V₂O₅–PVAc fibres are obtained. Calcination gradually removes PVAc and promotes structural rearrangement with consequent fibre‐morphology changes. With increasing calcination temperature, the crystallinity degree of V₂O₅ improves and a more oxygen‐deficient substoichiometric surface layer forms. Calcination at 400 °C preserves the fibre integrity. Indeed, fibres calcined at this temperature appear as the most suitable ones for use as the active layer in gas‐sensing devices. Copyright © 2011 John Wiley & Sons, Ltd.     

Li‐, Sb‐ and Ta‐modified (K,Na)NbO3 nanopowder prepared via a water‐based sol–gel method

Stable Li‐, Sb‐ and Ta‐modified (K, Na)NbO₃ (LTS‐KNN) sol and gel were successfully prepared via an economical water‐based sol–gel method. Simultaneous thermogravimetry and differential scanning calorimetry (TG‐DSC) and X‐ray diffraction showed that organic compounds were eliminated and a pure perovskite phase formed around 600 °C. Transmission electron microscopy showed that the LTS‐KNN particle size was in the range of 11–34 nm after decomposition at 600 °C. Moreover, high performance LTS‐KNN ceramic was successfully prepared at a low sintering temperature of 1000 °C by use of the nanopowder, and its room‐temperature d₃₃, K_p, K and loss are 311 pC/N, 46.8%, 1545 and 0.024, respectively. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ultra‐high long‐term stability of oxide‐TTFTs under current stress

In this letter the stability of transparent thin‐film transistors (TTFTs) based on the ZnO–SnO₂ (ZTO) material system is investigated. Bottom‐gate devices have been subject to electrical stress via a gate–source bias of 10 V and a drain‐source bias of 10 V leading to a drain–source current of 188 µA. In optimized TTFTs with a composition of [Zn]:[Sn] = 36:64 the relative change of the saturated field effect mobility was less than 1% and the threshold voltage shift was about 320 mV after 1000 hours of operation. This extraordinary stability of ZTO TTFTs underlines their suitability as drivers in active matrix OLED displays. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First‐principles study of the electronic structure and the associated magnetism of carbon‐doped TiO2

Based on first‐principles calculations, the electronic structure and the associated magnetism of carbon‐doped rutile TiO₂ have been investigated in the frame of the generalized gradient approximation (GGA). We find that the carbon substitutional oxygen ions can induce a magnetic moment of about 2.0µ_B/C, but the carbon substitutional titanium cannot provide any magnetism. Graphics of the spin density show that the magnetism is from the structure distortion around the carbon substitutional oxygen ions in the (110) plane of primitive TiO₂. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface passivation schemes for high‐efficiency n‐type Si solar cells

An effective passivation on the front side boron emitter is essential to utilize the full potential of solar cells fabricated on n‐type silicon. However, recent investigations have shown that it is more difficult to achieve a low surface recombination velocity on highly doped p‐type silicon than on n‐type silicon. Thus, the approach presented in this paper is to overcompensate the surface of the deep boron emitter locally by a shallow phosphorus diffusion. This inversion from p‐type to n‐type surface allows the use of standard technologies which are used for passivation of highly doped n‐type surfaces. Emitter saturation current densities (J_0e) of 49 fA/cm² have been reached with this approach on SiO₂ passivated lifetime samples. On solar cells a certified conversion efficiency of 21.7% with an open‐circuit voltage (V_oc) of 676 mV was achieved. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Calibration method at the N K‐edge using interstitial nitrogen gas in solid‐state nitrogen‐containing inorganic compounds

The standard method of soft X‐ray beamline calibration at the N K‐edge uses the ν = 0 peak transition of gas‐phase N₂. Interstitial N₂ gas trapped or formed within widely available solid‐state ammonium‐ and amine‐containing salts can be used for this purpose, bypassing gas‐phase measurements. Evidence from non‐nitrogen‐containing compounds (KH₂PO₄) and from He‐purged ammonium salts suggest that production of N₂ gas is through beam‐induced decomposition. Compounds with nitrate or nitrite as anions produce coincident features and are not suitable for this calibration method.     

Kinetics of photo‐darkening and self‐bleaching in amorphous As2S3 and As2Se3 thin films

The kinetics of photo‐darkening of amorphous As₂S₃ and a‐As₂Se₃ thin films follows a single exponential, but the magnitude and the rate of the process is higher in case of As₂S₃. The kinetics of self‐bleaching (dark relaxation) in advance photo‐darkened state follows a stretched exponential (SRE) with different stretching parameter for a‐As₂S₃ and a‐As₂Se₃. Within the J. C. Phillips approach we suppose that photo‐darkening in amorphous As₂S₃ films is, to some extent, accompanied by changes in short‐range order interactions, while photo‐darkening of amorphous As₂Se₃ is accompanied rather by changes in Coulomb interactions. The self‐bleaching process reduced the magnitude of photo‐darkening up to 45% and 60% for amorphous As₂S₃ and As₂Se₃ films, respectively. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)