Understanding the interaction of group V impurities with intrinsic defects in ZnO is important for developing p-type material. We have studied N-doped ZnO thin films and N-doped bulk ZnO crystals, with positron annihilation spectroscopy, in contrast to earlier studies that have concentrated on N-implanted ZnO crystals. We show that the introduction of N impurities into ZnO, irrespective of whether it is done during the growth of thin films or bulk crystals or through implantation and subsequent thermal treatments, leads to the formation of stable vacancy clusters and negative ion-type defects. Interestingly, the stability of these vacancy clusters is found almost exclusively for N introduction, whereas single Zn vacancy defects or easily removable vacancy clusters are more typically found for ZnO doped with other impurities.

Bulk-heterojunction organic photovoltaic (BHJ-OPV) technology promises high efficiency at ultralow cost and weight, with potential for nontraditional applications such as building-integrated photovoltaic (PV). There is a widespread presumption that the complexity of morphology makes carrier transport in OPV irreducibly complicated and, possibly, beyond predictive modeling. However, understanding the complex morphology is important because it not only dictates cell efficiency but also the panel performance and the operating lifetime. In this paper, we derive the fundamental thermodynamic as well as morphology-specific practical limits of BHJ-OPV efficiency and lifetime. We find that performance improvement relies not only on morphology engineering but also on increasing the effective mobility–lifetime (μτ) product, the cross-gap between donor/acceptors, and reducing the series resistance. Even if the OPV fails to achieve the highest efficiency anticipated by the thermodynamic limit, its novel form factor, lightweight, and transparency can make it a commercially viable option for many applications.

Nanocrystalline (NC) metals are known for having excellent strength but perceived to have poor ductility. Miniature tensile tests on NC Ni–Fe measured ultimate strengths of 2 GPa and elongations, by digital image correlation, of up to 10%. Detailed examination of the fracture surface revealed dimpled rupture and cross-section reduction up to 75%, suggesting an intrinsic ability for small grained Ni–Fe to accommodate plasticity. A survey of published studies on NC metals reveals that this behavior is quite common; despite low macroscopic elongation, NC metals often achieve extensive deformation suggesting good intrinsic ductility. Unfortunately, the common sheet-like configuration of NC tensile specimens muddies a simple evaluation of ductility based on elongation, since thin and wide geometries promote localized necking that expedites catastrophic failure. This paper presents a compact review of ductility concepts and literature to interpret the experimental ductility measurements of an electrodeposited nickel alloy.

Three-dimensional (3D) chrysanthemum-like carbon nanofiber (CCNF) foam architectures were synthesized on highly porous nickel foam via a one-step ambient pressure chemical vapor deposition process by introducing a mixture of precursor gases (H2 and C2H2). The as-synthesized 3D foam architectures were characterized by scanning electron microscopy and transmission electron microscopy, which demonstrate high porosity and a densely packed nature of the hierarchical carbon nanostructures. Symmetrical electrochemical double-layer capacitors were fabricated using electrodes based on the CCNF foam architectures. Cyclic voltammetry, charge–discharge measurements, and electrochemical impedance spectroscopy were conducted to determine the performance metrics. The supercapacitors (SCs) demonstrate a high areal capacitance of 1.37 F/cm2 (gravimetric specific capacitance: 23.83 F/g), which leads to superior values for per area energy density (0.19 Wh/cm2) and power density (141.77 W/cm2). In addition, capacitance retention of ∼100% over 13,000 charge–discharge cycles demonstrates the high electrochemical stability of this type of carbon nanostructure foam for high areal capacitance SCs.

Electronic devices made from single crystal thin films attached to inexpensive support substrates offer reduced material costs compared to wafer-based devices; however, scalable and inexpensive processes for producing these single crystal film structures have remained elusive. In this work, we describe a new approach for fabricating these structures. In our approach, an epitaxial film is grown on a single crystal template and is then separated from its growth surface via fracture along a weak heteroepitaxial interface between the single crystal film and its growth substrate. We show that epitaxial films of Si, Ge, and GaAs, with thicknesses ranging from 100 nm to 1 μm, grown on epitaxial CaF2 overlayers on Si <111> substrates, can be transferred to glass substrates by inducing fracture along the heteroepitaxial interface between the semiconductor film and CaF2, or between CaF2 and the Si wafer, assisted by the presence of water as in moisture-assisted cracking.

This article reviews the use of x-ray computed tomography (XRCT) to investigate the structure and properties of cellular solids. In the first section, the possibilities offered by XRCT are presented. Examples of tomographic images are shown for the three classes of material (polymers, metals, and ceramics). Different characterizations of cellular solids performed thanks to XRCT images are shown: calculation of morphological parameters, in situ and ex situ mechanical tests, and use of the tomographic images to perform finite element (FE) modeling. The second part of the paper presents the existing methods to create the meshes from tomographic images and highlights some interesting results from the FE simulations.

Red and near-infrared photons of longer wave lengths are poorly absorbed in thin film silicon cells and advanced light trapping methods are necessary. The physical mechanisms underlying the light trapping using periodic back reflectors are strong light diffraction, coupled with plasmonic light concentration. These are contrasted with the scattering mechanisms in randomly textured back reflectors. We describe a class of conformal solar cells with nanocone back reflectors with absorption at the Lambertian 4n2 limit, averaged over the “entire” wave length range for hydrogenated nanocrystalline silicon (nc-Si:H) thin-film solar cells. The absorption is theoretically found for 1-μm nc-Si:H cells, and is further enhanced for off-normal incidence. Predicted currents exceed 31 mA/cm2. Nc-Si:H solar cells with the same device architecture were conformally grown on periodic substrates and compared with randomly textured substrates. The periodic back reflector solar cells with nanopillars demonstrated higher quantum efficiency and photocurrents that were 1 mA/cm2 higher than those for the randomly textured back reflectors.

High-quality epitaxial silicon thin films have been deposited by plasma-enhanced chemical vapor deposition (PECVD) at 200 °C in a standard radiofrequency (RF) PECVD reactor. We optimized a silicon tetrafluoride (SiF4) plasma to clean the surface of <100> crystalline silicon wafers and without breaking vacuum, an epitaxial silicon film was grown from SiF4, hydrogen (H2), and argon (Ar) gas mixtures. We demonstrate that the H2/SiF4 flow rate ratio is a key parameter to grow high-quality epitaxial silicon films. Moreover, by changing this ratio, we can fine-tune the composition of the interface between the crystalline silicon (c-Si) wafer and the epitaxial film. In this way, at low values of the H2/SiF4 flow rate ratio, an abrupt interface is achieved. On the contrary, by increasing this ratio we can obtain a porous and fragile interface layer, composed of hydrogen-rich microcavities, which allows the transfer of the epitaxial film to foreign substrates.

To obtain highly dispersed and active Pd/C catalysts for formic acid electro-oxidation (FAEO), carbon supported Pd nanoparticles were prepared by three different synthesis methods. The first Pd deposition technique went through the ethylene glycol (EG)-assisted sodium borohydride (NaBH4) reduction process (Pd/C-EG-NaBH4). The second method was the polyol process (Pd/C-EG). The third method was the general NaBH4 reduction process (Pd/C-NaBH4). The results of x-ray diffraction and transmission electron microscopy (TEM) show that the Pd particles on carbon black prepared by the first method have the smallest average size of 3.5 nm with a narrow size distribution. Cyclic voltammetry was used to characterize the electrochemical performance. The peak current density (mass activity) of the Pd/C-EG-NaBH4 for FAEO is 1742 mA/mgPd, which is 1.45 times higher than that of Pd/C-EG and 1.48 times higher than that of Pd/C-NaBH4. Moreover, the experimental results show that the first method has no dependence on the pH value of the synthesis procedure, while the other two methods in the literature are greatly affected by the pH value.

Heteroepitaxial Ge quantum dots were grown on Si (001) by molecular beam epitaxy, with a Mn co-deposition flux giving a nominal composition of Ge0.9Mn0.1. At this large Mn flux, and with growth temperatures of 450 °C required for Ge quantum dot self-assembly, extensive second phase formation occurred. Atomic force microscopy reveals that quantum dots typical for the Ge/Si (001) system still form. In addition, copious formation of both rod-like and cluster-like morphologies is observed, with many of these structures conjoined to Ge dots. Extensive transmission electron microscopy identified several coexisting intermetallic phases, all based on Mn–silicide crystal structures, albeit with varying degrees of Ge substitution. The Ge quantum dots themselves appear to have little or no Mn incorporated in them, indicating that the intermetallic particles scavenge Mn from extended surface areas. Under these growth conditions, Mn is highly mobile, with surface diffusion lengths of the order of 800 nm, with significant bulk mobility as well, resulting in surface structures that also penetrate the Si substrate. A magnetic phase transition at 220 °C does not match known behavior of the bulk silicide phases but might result from extensive ternary alloying with Ge, especially into the cubic MnSi phase.

Density functional theory, which can be used for simulating the properties of materials in the electronic ground state, was extended to time-dependent density functional theory (TDDFT). This extension enabled us to simulate nonthermal (nonequilibrium) dynamics under electronic excitation as well as to analyze and predict phenomena observed in experiments using femtosecond lasers. In this invited paper, a numerical simulation based on TDDFT for laser-induced dynamics of molecules encapsulated in carbon nanotubes (CNTs) is presented. Fast motion of molecules can be induced by short strong laser pulses that cause electronic excitation. The role of CNTs is not simply trapping the molecules but also modulating the electric field of the laser pulse. This knowledge of microscopic-scale processes will be useful when using CNTs as nanoscale test tubes in future photochemistry experiments in confined spaces for the synthesis of exotic materials. The numerical scheme and detailed results of the simulation are also presented here.

The paper established a model to investigate the interaction between the special rotational deformation and a semielliptical blunt crack in deformed nanocrystalline materials. By using the complex variable method, the effect of a disclination quadrupole produced by the special rotational deformation on the emission of lattice dislocation from a semielliptical blunt crack tip was explored theoretically. The complex form expression of the dislocation force was derived, and the critical stress intensity factors (SIFs) for the first edge dislocation emission were calculated. Then, the influence of the disclination strength, the disclination location and orientation, the special rotational deformation orientation, the grain size, and the curvature radius of blunt crack tip on the critical SIFs were discussed in detail, and a comparison with the sharp crack behavior was presented. The results show that the special rotational deformation and the curvature radius of blunt crack have great effects on the lattice dislocation emission form blunt crack tip. Some influence laws are also different with those of the edge dislocation emission from a sharp crack tip.

The indole molecularly imprinted polymer (indole-MIP) was synthesized by atom transfer radical emulsion polymerization (ATREP). The novel adsorbent was used to adsorb indole from fuel oil. The indole-MIP had a high selectivity to indole, and the mass transfer limitations were overcome. The property and morphology of indole-MIP were described by a series of characterization methods. A great specific area and more pores of indole-MIP were shown. The static adsorption experiments display that equilibrium adsorption capacity of indole-MIP was 34.488 mg/g. The adsorption process was spontaneous by thermodynamic analysis, and a dense mass of indole was adsorbed onto indole-MIP at a proper low temperature (298 K). Pseudo-second-order kinetic model was more fitted with experimental data. Both Langmuir and Freundlich isotherm models were obeyed by adsorption isotherm test. The selective and competitive performances of indole-MIP were favorable, and the regeneration capacity was appreciable.

New strategies for materials fabrication are of fundamental importance in the advancement of science and technology. Nanocrystals, especially with an anisotropic shape such as cubic, are candidates for building blocks for new bottom-up approaches to materials assembly, yielding a functional architecture. Such materials also receive attention because of their intrinsic size-dependent properties and resulting applications. Here, we report synthesis and characteristics of BaTiO3 and SrTiO3 nanocubes and the ordered assemblies as ferroelectric supracrystals. BaTiO3 and SrTiO3 nanocubes with narrow size distributions were obtained in an aqueous process. BaTiO3 films made up of ordered nanocube assemblies were fabricated on various substrates by evaporation-induced self-assembly method. Regardless of the substrate, the nanocubes exhibited {100} orientations and a high degree of face-to-face ordering, which remained even after heat treatment at 850 °C. Piezoresponse force microscopy was carried out on the supracrsytal films to obtain plots of the d33 piezoelectric coefficient against the poling field, and ferroelectric hysteresis curves were shown.

Advances in nanotechnology have prompted rapid progress and versatile imaging modalities for diagnostics and treatment of diseases. Molecular imaging is a powerful technique for quantifying physiological changes in vivo using noninvasive imaging probes. These probes are used to image specific cells and tissues within a whole organism. Currently, imaging is an essential part of clinical protocols providing morphological, structural, metabolic and functional information. Using theranostic micro- or nanoparticles, which combine both therapeutic and diagnostic capabilities in one single entity, holds a true promise to propel the biomedical field toward personalized medicine. With this approach, biological processes can be directly and simultaneously monitored with the treatment of the diseases. This mini-review highlights the recent innovative diagnostic imaging aspects of porous silicon (PSi) materials and emphasizes their potential as theranostic platforms and tools for the clinic. Multiple biomedical imaging applications of the PSi materials are also outlined.

This paper describes the use of self-patterning anodic aluminum oxide (AAO) layers to enable localized metal contacts and to achieve passivation for the rear surface of silicon solar cells. There are no commercially available technologies that are capable of patterning localized contacts on silicon solar cells with low cost, high-throughput, and robust processing, especially when closely spaced small-area openings are required. In the approach described, nanoporous AAO layers were formed by anodizing aluminum over intervening dielectrics on textured silicon wafers. When the anodized test structures were fired in a belt furnace, localized contacts formed at peaks and valleys of the alkaline-textured silicon surface. Furthermore, the anodization contributed ∼35 mV increment in the implied Voc of the test structures. Low contact resistivity was demonstrated and the proposed contacting mechanism for this innovative localization suggested that the contact percentage can be controlled by varying the anodization duration and/or the surface morphology.

The considerable potential of model-type thin film electrodes for the investigation of oxygen exchange pathways is demonstrated for different electrode materials on yttria-stabilized zirconia (YSZ). In particular, a correlation of voltage-driven 18O tracer experiments and electrical ac and dc measurements has proven to be helpful when aiming at mechanistic conclusions. For Pt electrodes, two different parallel reaction pathways can be identified under equilibrium conditions. At lower temperatures, a diffusion limited path through the electrode is dominant, whereas at higher temperatures, an electrode surface path with oxygen incorporation at the three-phase boundary determines the electrochemical activity. In addition, for high cathodic polarization, an electrolyte surface path with electron transfer via YSZ outperforms both other pathways. The oxygen incorporation zones of the bulk path as well as the electrolyte surface path can be visualized by 18O tracer incorporation experiments in combination with time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis. A successful separation of surface and bulk path can also be obtained for La0.8Sr0.2MnO3−δ (LSM) electrodes by means of 18O tracer incorporation at different cathodic overpotentials. Under lower polarization, a surface path with oxygen incorporation at the three-phase boundary is dominant, whereas at higher cathodic overpotential, the bulk path becomes significantly more pronounced. These changes are discussed in terms of polarization-induced changes of the ionic conductivity in the LSM electrode. Measurements on the acceptor-doped perovskite-type materials La0.6Sr0.4CoO3−δ (LSC) and La0.6Sr0.4FeO3−δ (LSF) illustrate the limitations of the tracer incorporation method. In the case of highly active LSC electrodes with low polarization resistances, the tracer distribution is determined by the electrolyte, and thus the active sites of the electrodes can no longer be visualized. The effect of polarization-induced changes of the electrode's electronic conductivity is demonstrated for LSF. Only a region close to the current collector remains electrochemically active owing to limited lateral electron transport.

An extended version of self-consistent field (SCF) theory that was recently introduced by the authors [Li et al., J. Chem. Phys.137, 024906, (2012)] is used to study the phase behavior of a polymer blend with reversible crosslinks. The system consists of symmetric AB diblock copolymers and homopolymers of type A and B. We consider reversible crosslinks that can form between the diblock copolymers with a crosslink strength z and crosslink weights ωA and ωB for monomers of type A and B, respectively. Crosslinks between homopolymers are disabled. We present a phase diagram as a function of the A fraction of homopolymers $\phi _{\rm{\alpha }}^{{\rm{rel}}}$, the crosslink strength z, and the crosslink asymmetry ∆ω = ωA − ωB. A hexagonal phase is found for suitably large $\phi _{\rm{\alpha }}^{{\rm{rel}}}$, and suitably small z and $\left| {\Delta {\rm{\omega }}} \right|$. Otherwise the system forms a lamellar phase. A deeper insight into the phase behavior is gained from analyzing the free energy contributions in the hexagonal and the lamellar phase with the help of the capabilities of the extended SCF theory developed by us.