Reversible nanoscale switching of polytwin orientation in a ferroelectric thin film induced by a local electric field

The response to a local, tip-induced electric field of ferroelastic domains in thin polycrystalline lead zirconate titanate films with predominantly (110) orientation has been studied using Enhanced Piezoresponse Force Microscopy. Two types of reversible polytwin switching between well-defined orientations have been observed. When a-c domains are switched to other forms of a-c domains, the ferroelastic domain walls rotate in-plane by 109.5°, and when a-c domains are switched to c-c domains (or vice-versa), the walls rotate by 54.75°. © 2013 AIP Publishing LLC.

The influence of 1D, meso- and crystal structures on charge transport and recombination in solid-state dye-sensitized solar cells

We have prepared single crystalline SnO2 and ZnO nanowires and polycrystalline TiO2 nanotubes (1D networks) as well as nanoparticle-based films (3D networks) from the same materials to be used as photoanodes for solid-state dye-sensitized solar cells. In general, superior photovoltaic performance can be achieved from devices based on 3-dimensional networks, mostly due to their higher short circuit currents. To further characterize the fabricated devices, the electronic properties of the different networks were measured via the transient photocurrent and photovoltage decay techniques. Nanowire-based devices exhibit extremely high, light independent electron transport rates while recombination dynamics remain unchanged. This indicates, contrary to expectations, a decoupling of transport and recombination dynamics. For typical nanoparticle-based photoanodes, the devices are usually considered electron-limited due to the poor electron transport through nanocrystalline titania networks. In the case of the nanowire-based devices, the system becomes limited by the organic hole transporter used. In the case of polycrystalline TiO2 nanotube-based devices, we observe lower transport rates and higher recombination dynamics than their nanoparticle-based counterparts, suggesting that in order to improve the electron transport properties of solid-state dye-sensitized solar cells, single crystalline structures should be used. These findings should aid future design of photoanodes based on nanowires or porous semiconductors with extended crystallinity to be used in dye-sensitized solar cells. © 2013 The Royal Society of Chemistry.

Grain boundary interface mechanics in strain gradient crystal plasticity

Interactions between dislocations and grain boundaries play an important role in the plastic deformation of polycrystalline metals. Capturing accurately the behaviour of these internal interfaces is particularly important for applications where the relative grain boundary fraction is significant, such as ultra fine-grained metals, thin films and microdevices. Incorporating these micro-scale interactions (which are sensitive to a number of dislocation, interface and crystallographic parameters) within a macro-scale crystal plasticity model poses a challenge. The innovative features in the present paper include (i) the formulation of a thermodynamically consistent grain boundary interface model within a microstructurally motivated strain gradient crystal plasticity framework, (ii) the presence of intra-grain slip system coupling through a microstructurally derived internal stress, (iii) the incorporation of inter-grain slip system coupling via an interface energy accounting for both the magnitude and direction of contributions to the residual defect from all slip systems in the two neighbouring grains, and (iv) the numerical implementation of the grain boundary model to directly investigate the influence of the interface constitutive parameters on plastic deformation. The model problem of a bicrystal deforming in plane strain is analysed. The influence of dissipative and energetic interface hardening, grain misorientation, asymmetry in the grain orientations and the grain size are systematically investigated. In each case, the crystal response is compared with reference calculations with grain boundaries that are either 'microhard' (impenetrable to dislocations) or 'microfree' (an infinite dislocation sink). © 2013 Elsevier Ltd. All rights reserved.

Superhydrophobic carbon nanotube electrode produces a near-symmetrical alternating current from photosynthetic protein-based photoelectrochemical cells

The construction of protein-based photoelectrochemical cells that produce a variety of alternating currents in response to discontinuous illumination is reported. The photovoltaic component is a protein complex from the purple photosynthetic bacterium Rhodobacter sphaeroides which catalyses photochemical charge separation with a high quantum yield. Photoelectrochemical cells formed from this protein, a mobile redox mediator and a counter electrode formed from cobalt disilicide, titanium nitride, platinum, or multi-walled carbon nanotubes (MWCNT) generate a direct current during continuous illumination and an alternating current with different characteristics during discontinuous illumination. In particular, the use of superhydrophobic MWCNT as the back electrode results in a near symmetrical forward and reverse current upon light on and light off, respectively. The symmetry of the AC output of these cells is correlated with the wettability of the counter electrode. Potential applications of a hybrid biological/synthetic solar cell capable of generating an approximately symmetrical alternating current are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.