Characterizing ion dynamics in nanoscopic volumes: time-domain electrostatic force spectroscopy on solid electrolytes

Abstract  We use time-domain electrostatic force spectroscopy (TD-EFS) for characterizing the ion dynamics in solid electrolytes on a nanoscopic level. For partially crystallized glass ceramics we are able to distinguish between dynamic processes in the glassy phase, in crystallites, and at interfaces. Nanoscopic polarization spots can be created and directly visualized, and their time evolution can be studied. By applying grid-type spectroscopic measurements, maps of the local relaxation strength can be obtained, giving information about the spatial distribution of the glassy and crystalline phases. Graphical abstract        

Electronic properties of the metal/organic interlayer/inorganic semiconductor sandwich device

In this study, we prepared a Metal(Al)/Organic Interlayer(Congo Red=CR)/Inorganic Semiconductor (p-Si) (MIS) Schottky device formed by coating of an organic film on p-Si semiconductor wafer. The Al/CR/p-Si MIS device had a good rectifying behavior. By using the forward bias I-V characteristics, the values of ideality factor (n) and barrier height (Φ_b) for the Al/CR/p-Si MIS device were obtained as 1.68 and 0.77 eV, respectively. It was seen that the Φ_b value of 0.77 eV calculated for the Al/CR/p-Si MIS device was significantly higher than value of 0.50 eV of the conventional Al/p-Si Schottky diodes. Modification of the interfacial potential barrier of the Al/p-Si diode was achieved by using a thin interlayer of the CR organic material. This was attributed to the fact that the CR organic interlayer increased the effective barrier height by influencing the space charge region of Si. The interface-state density of the MIS diode was found to vary from 1.24×10¹³ to 2.44×10¹² eV⁻¹ cm⁻².     

A mesoscopic model of the intermixing during nanoenergetic materials processing

A general mesoscopic model for the simulation of thin-film vapor deposition applied to energetic materials, specifically bimetallic multilayers, is presented. We describe the setup of this mesoscopic simulator developed in the frame of a multiscale study by implementing ab initio data into a set of differential equations. We present numerical results relative to the formation of barrier layers as a result of interdiffusion between successive bimetallic AlNi multilayers. The key role of the vacancies species created during deposition is highlighted.     

Fabrication of Ru(bpy)3-titanate nanotube nanocomposite and its application as sensitive solid-state electrochemiluminescence sensor material

A novel and facile method for effective immobilization of Ru(bpy)₃²⁺ within titanate nanotubes (TiNTs) and its application as a sensitive solid-state electrochemiluminescence (ECL) sensor material was studied. The process involved the formation of Ru(bpy)₃²⁺-titanate nanotube nanocomposite (Ru-TiNTs) via electrostatic interactions by mixing TiNTs and Ru(bpy)₃(ClO₄)₂ in aqueous medium. Then Ru-TiNTs were attached to the surface of a Pt electrode to form an ECL sensor. Characterization of Ru(bpy)₃²⁺-titanate nanotube nanocomposite was accomplished by transmission electron microscopy, X-ray photoelectron spectrum, and field emission scanning electron microscope. The electrochemistry and ECL behavior of Ru(bpy)₃²⁺ immobilized on TiNTs were studied with tripropylamine as a coreactant. As-prepared Ru-TiNTs exhibited very good stability and Ru(bpy)₃²⁺ species contained showed excellent ECL behavior. Therefore, the as-prepared Ru(bpy)₃²⁺-titanate nanotube nanocomposite exhibited great promise as new luminescent materials for solid-state ECL detection.     

A new apparatus for testing the delayed mechanical behaviour of interfaces: The Shearing Interfaces Creep box (SInC box)

A new experimental apparatus is presented for testing the time-dependent behaviour of interfaces, including in particular interfaces of geomaterials, under constant loading. This apparatus allows the application of two orthogonal loads normal and tangential to the mean plane of the interface, as well as the measurement of the axial and tangential relative displacements. The sample is moulded inside two half shear boxes and the system is designed in such a way that the shear force is applied along the mean plane of the interface. Some preliminary testing was carried out on a clay rock/concrete interface, under a controlled temperature environment. Preliminary results are presented, showing the evolution of the delayed displacements.     

The influence of the growth temperature and interruption time on the crystal quality of InGaAs/GaAs QW structures grown by MBE and MOCVD methods

The impact of two technological parameters, i.e., the growth temperature and the interface growth interruption, on the crystal quality of strained InGaAs/GaAs quantum well (QW) structures was studied. The investigated heterostructures were grown by molecular beam epitaxy (MBE) and metalorganic chemical vapour deposition (MOCVD) under As-rich conditions. Photoluminescence (PL), reflection high-energy electron diffraction (RHEED) and atomic force microscopy (AFM) were adopted for the evaluation of specified interfaces smoothness and the quality of layers. Comparison between both epitaxial techniques allowed us to find, that the growth temperature plays more significant role in the case of structures grown by MBE technique, whereas the quality of MOCVD grown structures is more sensitive to the growth interruption. Optimum values of the investigated parameters of QW crystallization were obtained for both growth techniques.     

Interfacial Roughening in Field Theory

In the rough phase, the width of interfaces separating different phases of statistical systems increases logarithmically with the system size. This phenomenon is commonly described in terms of the capillary wave model, which deals with fluctuating, infinitely thin membranes, requiring ad hoc cut-offs in momentum space. We investigate the interface roughening in a unified approach, which does not rely on joining different models, namely in the framework of the Landau-Ginzburg model, that is renormalized field theory, in the one-loop approximation. The interface profile and width are calculated analytically, resulting in finite expressions with definite coefficients. They are valid in the scaling region and depend on the known renormalized coupling constant.     

A height–flux method for simulating free surface flows and interfaces

A new technique for the numerical simulation of the free surface flows is developed. This technique is based on the finite element method with penalty formulation, and a flux method for surface advection. The advection part which is completely independent of the momentum solver is based on subdividing the fluid domain into small subvolumes along one of the co-ordinate axis. The subvolumes are then used to find the height function which will later describe the free surface. The free surface of the fluid in each subvolume is approximated by a line segment and its slope is calculated using the volume of the fluid in the two neighbouring subvolumes. Later, the unidirectional volume flux from one subvolume to its neighbouring one is calculated using the conservation laws, and the new surface line segments are reconstructed. This technique, referred to as the Height–Flux Method (HFM) is implemented to simulate the temporal instability of a capillary jet. The results of the numerical simulation well predict the experimental data. It is also shown that the HFM is computationally more efficient than the techniques which use a kinematic boundary condition for the surface advection.     

Electron energy loss spectroscopy analysis of the interaction of Cr and V with MWCNTs

The presented scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) results show the strong reaction of Cr and V with the graphitic walls of MWCNTs. For Vanadium, an interfacial VC layer could be observed at the interface between VN and MWCNTs, when the samples were heated in situ to 750 °C. Knowledge about this interfacial VC layer is important for the formation of VN-MWCNT hybrid materials, used in supercapacitor electrodes, often synthesized at high temperatures. Chromium reacts at 500 °C with the MWCNTs to form Cr₃C₂ and in some cases, dissolved the MWCNT completely. Together with the previously published results about the interaction of MWCNTs with Cu (no interaction) and Ni (a slight rehybridisation trend for the outermost MWCNT-wall observed with EELS) (Ilari et al., 2015) the influence of the valence d-orbital occupancy of 3d transition metals on the interaction strength with CNTs is shown experimentally. For a transition metal to form chemical bonds towards CNT-walls, unoccupied states in its valence d-orbitals are needed. While Ni (2 unoccupied states) interacts only slightly, Cr (5 unoccupied states) and V (7 unoccupied states) react much stronger and can dissolve the MWCNTs, at least partially.     

Spatial Localization of Two Enzymes at Pickering Emulsion Droplet Interfaces for Cascade Reactions

Developing biocatalytic cascades in abiological conditions is of utmost significance, but such processes often suffer from low reaction efficiency because of incompatible reaction environments and suppressed intermediate transportation. Herein we report a new type of biocatalytic cascade by localizing two different enzymes separately in the outer and inner interfacial layers of Pickering emulsion droplets. This versatile approach enables the localization of two enzymes in their preferred reaction microenvironments and simultaneously in nanoscale proximity of each other. The thus-designed interfacial biocatalytic cascades show outstanding catalytic efficiency in alkene epoxidation and thioether oxidation with in situ generation of hydrogen peroxide under mild conditions, 6.9–13.6 times higher than the catalytic efficiency of the free enzymes in solution and their multi-enzymatic counterparts. The remarkable interfacial effect of Pickering droplets was found to be responsible for the significantly enhanced cascading efficiency.