Relaxing the Conductivity/Transparency Trade‐Off in MOCVD ZnO Thin Films by Hydrogen Plasma

Increasing the conductivity of polycrystalline zinc oxide films without impacting the transparency is a key aspect in the race to find affordable and high quality material as replacement of indium‐containing oxides. Usually, ZnO film conductivity is provided by a high doping and electron concentration, detrimental to transparency, because of free carrier absorption. Here we show that hydrogen post‐deposition plasma treatment applied to ZnO films prepared by metalorganic low‐pressure chemical vapor deposition allows a relaxation of the constraints of the conductivity/transparency trade‐off. Upon treatment, an increase in electron concentration and Hall mobility is observed. The mobility reaches high values of 58 and 46 cm²V^?1s^?1 for 2‐μm‐ and 350‐nm‐thick films, respectively, without altering the visible range transparency. From a combination of opto‐electronic measurements, hydrogen is found, in particular, to reduce electron trap density at grain boundaries. After treatment, the values for intragrain or optical mobility are found similar to Hall mobility, and therefore, electron conduction is found to be no longer limited by the phenomenon of grain boundary scattering. This allows to achieve mobilities close to 60 cm²V^?1s^?1, even in ultra‐transparent films with carrier concentration as low as 10¹⁹ cm^?3.     

Uncertainty assessment for the airborne nanoparticle collection efficiency of a TEM grid-equipped sampling system by Monte-Carlo calculation

A mini particle sampler (MPS) equipped with a transmission electron microscopy (TEM) grid enables convenient particle sampling to subsequent analysis. However, its sampling efficiency involves uncertainties, and accurate sampling efficiency is required for particle collection applications. In this study, the sampling efficiency uncertainties from measured data and models are quantified using Monte-Carlo methods. The Sobol variance-based sensitivity analysis is used to determine the contributions of parameters to the sampling efficiency uncertainties. The results reveal that the sampling efficiency uncertainties from experimental dispersion calibration and theoretical models are generally less than 1% and 9%, respectively. Most sampling efficiency measured data are covered by the efficiency uncertainty range simulated by theoretical models. Pore size and flowrate contribute significantly to the sampling efficiency uncertainties and require control to improve the sampling efficiency precision. Besides, the Cunningham correction factor is also a sensitivity parameter. The utilization of proper models is crucial to support simulations for further process optimization. This study offers a quantitative method for nanoparticle collection efficiency analysis, which will help assess nanomaterials’ workplace exposure.     

Generalization of <Emphasis Type=Italic>T</Emphasis> and <Emphasis Type=Italic>A</Emphasis> integrals to time-dependent materials: analytical formulations

This paper deals with the generalization of T-integral to crack growth process in viscoelastic materials. In order to implement this expression in a finite element software, a modelling form of this integral, called Aθ, is developed. The analytical formulation is based on conservative law, independent path integral, and a combination of real, virtual displacement fields, and real, virtual thermal fields introducing, in the same time, a bilinear form of free energy density F. According to the generalization of Noether’s method, the application of Gauss Ostrogradski’s theorem combined with curvilinear cracked contour, T _v is obtained. By introducing a volume domain around crack tip, the modelling expression Aθ is also defined.. Finally, the viscoelastic generalization through a thermodynamic approach, called A _v , is introduced by using a discretisation of the creep tensor according to a generalized Kelvin Voigt representation.     

Laser synthesized TiO2-based nanoparticles and their efficiency in the photocatalytic degradation of linear carboxylic acids

Abstract

Titanium dioxide nanoparticles were synthesized by laser pyrolysis, their surface and electronic properties were modified by gold and/or nitrogen. These materials were characterized by different techniques like X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Time resolved conductivity (TRMC) was used to study the charge separation of electron/hole pairs. Altogether (XPS, EPR, TRMC), the physicochemical characterizations are well correlated with chemical photoactivity of the different samples. Their photocatalytic activity was evaluated for the degradation of linear carboxylic acids (C2-C3) under UV and visible illumination. The decomposition rate of acids was measured, it shows that the modification with gold increases the photoactivity while the presence of nitrogen slows down the process. Such observations are in good agreement with evolution of TRMC signals. A degradation pathway has been determined by identification of intermediate products by chromatography and EPR, results show different intermediate species. In particular EPR confirms the presence of NO^2? paramagnetic centers and shows two novel N centered paramagnetic centers. A decrease of the degradation rate is observed with increase of carboxylic acid chain length.     

Synthesis of biomolecule-modified mesoporous silica nanoparticles for targeted hydrophobic drug delivery to cancer cells

Synthetic methodologies integrating hydrophobic drug delivery and biomolecular targeting with mesoporous silica nanoparticles are described. Transferrin and cyclic-RGD peptides are covalently attached to the nanoparticles utilizing different techniques and provide selectivity between primary and metastatic cancer cells. The increase in cellular uptake of the targeted particles is examined using fluorescence microscopy and flow cytometry. Transferrin-modified silica nanoparticles display enhancement in particle uptake by Panc-1 cancer cells over that of normal HFF cells. The endocytotic pathway for these particles is further investigated through plasmid transfection of the transferrin receptor into the normal HFF cell line, which results in an increase in particle endocytosis as compared to unmodified HFF cells. By designing and attaching a synthetic cyclic-RGD, selectivity between primary cancer cells (BT-549) and metastatic cancer cells (MDA-MB 435) is achieved with enhanced particle uptake by the metastatic cancer cell line. Incorporation of the hydrophobic drug Camptothecin into these two types of biomolecular-targeted nanoparticles causes an increase in mortality of the targeted cancer cells compared to that caused by both the free drug and nontargeted particles. These results demonstrate successful biomolecular-targeted hydrophobic drug delivery carriers that selectively target specific cancer cells and result in enhanced drug delivery and cell mortality.     

Nonlinear fluid–structure interaction problem. Part I: implicit partitioned algorithm,nonlinear stability proof and validation examples

In this work we consider the fluid-structure interaction in fully nonlinear setting, where different space discretization can be used. The model problem considers finite elements for structure and finite volume for fluid. The computations for such interaction problem are performed by implicit schemes, and the partitioned algorithm separating fluid from structural iterations. The formal proof is given to find the condition for convergence of this iterative procedure in the fully nonlinear setting. Several validation examples are shown to confirm the proposed convergence criteria of partitioned algorithm. The proposed strategy provides a very suitable basics for code-coupling implementation as discussed in Part II.     

Heavy metals uptake by sonicated activated sludge: relation with floc surface properties

The effects of sonication of activated sludge on heavy metal uptake were in a first time investigated in respect with potential modifications of floc surface properties. The treatment led to the simultaneous increase of specific surface area and of the availability of negative and/or hydrophilic sites. In parallel, organic matter was released in the soluble fraction. Sorption isotherms of cadmium and copper showed that uptake characteristics and mechanisms were highly dependent on both heavy metal species and specific energy supplied. The increase of both specific surface area and fixation sites availability led to the increase of Cd(II) uptake. For Cu(II), organic matter released in soluble phase during the treatment seemed to act as a ligand and to limit adsorption on flocs surface. Three different heavy metals uptake mechanisms have been identified: proton exchange, ion exchange and (co)precipitation.     

Designing bistable [2]rotaxanes for molecular electronic devices

The development of molecular electronic components has been accelerated by the promise of increased circuit densities and reduced power consumption. Bistable rotaxanes have been assembled into nanowire crossbar devices, where they may be switched between low- and high-conductivity states, forming the basis for a molecular memory. These memory devices have been scaled to densities of 10(11) bits cm(-2), the 2020 node for memory of the International Technology Roadmap for Semiconductors. Investigations of the kinetics and thermodynamics associated with the electromechanical switching processes of several bistable [2]rotaxane derivatives in solution, self-assembled monolayers on gold, polymer electrolyte gels and in molecular switch tunnel junction devices are consistent with a single, universal switching mechanism whose speed is dependent largely on the environment, as well as on the structure of the switching molecule. X-ray reflectometry studies of the bistable rotaxanes assembled into Langmuir monolayers also lend support to an oxidatively driven mechanical switching process. Structural information obtained from Fourier transform reflection absorption infrared spectroscopy of rotaxane monolayers taken before and after evaporation of a Ti top electrode confirmed that the functionality responsible for switching is not affected by the metal deposition process. All the considerable experimental data, taken together with detailed computational work, support the hypothesis that the tunnelling current hysteresis, which forms the basis of memory operation, is a direct result of the electromechanical switching of the bistable rotaxanes.     

Thermomechanical characterization of stress localization in glass: An experimental and numerical study

Thermoelastic stress analysis and quantitative calorimetry are full‐field noncontact techniques widely used to study the thermomechanical behaviour of materials. The first one linearly relates the sum of the principal stresses to the temperature variation, and the second one can be used to measure the mechanical dissipation. However, brittle materials such as glass are a priori bad candidates for these techniques. Indeed, their low‐temperature variations under loading lead to very noisy infrared images, and their brittle mechanical behaviour does not allow to deform them significantly. In the present paper, the thermomechanical characterization of a holed glass sample under cyclic loading is performed. A preliminary new filtering methodology has been applied to the thermal movie to remove the noise. The stress field obtained from the thermoelastic stress analysis is well correlated to the finite element model showing that this technique is adapted to study the thermoelastic response of brittle materials. Finally, the corresponding calorimetric response has been determined by using a simplified formulation of the heat diffusion equation. This permits to quantify heat sources and to carry out energy balances.     

Reticular exploration of uranium-based metal-organic frameworks with hexacarboxylate building units

The rational reticular design of metal-organic frameworks(MOFs)from building units of known geometries is essential for enriching the diversity of MOF structures.Unexpected and intriguing structures,however,can also arise from subtle changes in the rigidity/length of organic linkers and/or synthetic conditions.Herein,we report three uranium-based MOF structures—i.e.,NU-135X(X=0,1,2)—synthesized from trigonal planar uranyl nodes and triptycene-based hexacarboxylate ligands with variable arm lengths.A new chiral 3,6-connected nuc net was observed in NU-1350,while the extended versions of the ligand led to 3-fold catenated MOFs(NU-1351 and NU-1352)with rare 3,6-connected cml-c3 nets.The differences in the topology of NU-1350 and NU-1351/NU-1352 could be attributed to the slight distortions of the shorter linker in the former from the ideal trigonal prism geometry to an octahedral geometry when coordinated to the trigonal planar uranyl nodes.