An ignition key for atomic-scale engines

A current-carrying resonant nanoscale device, simulated by non-adiabatic molecular dynamics, exhibits sharp activation of non-conservative current-induced forces with bias. The result, above the critical bias, is generalized rotational atomic motion with a large gain in kinetic energy. The activation exploits sharp features in the electronic structure, and constitutes, in effect, an ignition key for atomic-scale motors. A controlling factor for the effect is the non-equilibrium dynamical response matrix for small-amplitude atomic motion under current. This matrix can be found from the steady-state electronic structure by a simpler static calculation, providing a way to detect the likely appearance, or otherwise, of non-conservative dynamics, in advance of real-time modelling.

Physical basis and biological mechanisms of gold nanoparticle radiosensitization

The unique properties of nanomaterials, in particular gold nanoparticles (GNPs) have applications for a wide range of biomedical applications. GNPs have been proposed as novel radiosensitizing agents due to their strong photoelectric absorption coefficient. Experimental evidence supporting the application of GNPs as radiosensitizing agents has been provided from extensive in vitro investigation and a relatively limited number of in vivo studies. Whilst these studies provide experimental evidence for the use of GNPs in combination with ionising radiation, there is an apparent disparity between the observed experimental findings and the level of radiosensitization predicted by mass energy absorption and GNP concentration. This review summarises experimental findings and attempts to highlight potential underlying biological mechanisms of response in GNP radiosensitization.

Hybrid FIB milling strategy for the fabrication of plasmonic nanostructures on semiconductor substrates

The optical properties of plasmonic semiconductor devices fabricated by focused ion beam (FIB) milling deteriorate because of the amorphisation of the semiconductor substrate. This study explores the effects of combining traditional 30 kV FIB milling with 5 kV FIB patterning to minimise the semiconductor damage and at the same time maintain high spatial resolution. The use of reduced acceleration voltages is shown to reduce the damage from higher energy ions on the example of fabrication of plasmonic crystals on semiconductor substrates leading to 7-fold increase in transmission. This effect is important for focused-ion beam fabrication of plasmonic structures integrated with photodetectors, light-emitting diodes and semiconductor lasers.

Ferroelectricity in Strain-Free SrTiO3 Thin Films

Biaxial strain is known to induce ferroelectricity in thin films of nominally nonferroelectric materials such as SrTiO3. By a direct comparison of the strained and strain-free SrTiO3 films using dielectric, ferroelectric, Raman, nonlinear optical and nanoscale piezoelectric property measurements, we conclude that all SrTiO3 films and bulk crystals are relaxor ferroelectrics, and the role of strain is to stabilize longerrange correlation of preexisting nanopolar regions, likely originating from minute amounts of unintentional Sr deficiency in nominally stoichiometric samples. These findings highlight the sensitive role of stoichiometry when exploring strain and epitaxy-induced electronic phenomena in oxide films, heterostructures, and interfaces.

Switchable Induced Polarization in LaAlO3/SrTiO3 Heterostructures

Demonstration of a tunable conductivity of the LaAlO3/SrTiO3 interfaces drew significant attention to the development of oxide electronic structures where electronic confinement can be reduced to the nanometer range. While the mechanisms for the conductivity modulation are quite different and include metal insulator phase transition and surface charge writing, generally it is implied that this effect is a result of electrical modification of the LaAlO3 surface (either due to electrochemical dissociation of surface adsorbates or free charge deposition) leading to the change in the two-dimensional electron. gas (2DEG) density at the LaAlO3/SrTiO3 (LAO/STO) interface. In this paper, using piezoresponse force microscopy we demonstrate a switchable electromechanical response of the LAO overlayer, which we attribute to the motion of oxygen vacancies through the LAO layer thickness. These electrically induced reversible changes in bulk stoichiometry of the LAO layer are a signature of a possible additional mechanism for nanoscale oxide 2DEG control on LAO/STO interfaces.

Ionically-Mediated Electromechanical Hysteresis in Transition Metal Oxides

Nanoscale electromechanical activity, remanent polarization states, and hysteresis loops in paraelectric TiO2 and SrTiO3 thin films are observed using scanning probe microscopy. The coupling between the ionic dynamics and incipient ferroelectricity in these materials is analyzed using extended Landau-Ginzburg-Devonshire (LGD) theory. The possible origins of electromechanical coupling including ionic dynamics, surface-charge induced electrostriction, and ionically induced ferroelectricity are identified. For the latter, the ionic contribution can change the sign of first order LGD expansion coefficient, rendering material effectively ferroelectric. The lifetime of these ionically induced ferroelectric states is then controlled by the transport time of the mobile ionic species and well above that of polarization switching. These studies provide possible explanation for ferroelectric-like behavior in centrosymmetric transition metal oxides.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Mimicking the colourful wing scale structure of the Papilio blumei butterfly

The brightest and most vivid colours in nature arise from the interaction of light with surfaces that exhibit periodic structure on the micro- and nanoscale. In the wings of butterflies, for example, a combination of multilayer interference, optical gratings, photonic crystals and other optical structures gives rise to complex colour mixing. Although the physics of structural colours is well understood, it remains a challenge to create artificial replicas of natural photonic structures(1-3). Here we use a combination of layer deposition techniques, including colloidal self-assembly, sputtering and atomic layer deposition, to fabricate photonic structures that mimic the colour mixing effect found on the wings of the Indonesian butterfly Papilio blumei. We also show that a conceptual variation to the natural structure leads to enhanced optical properties. Our approach offers improved efficiency, versatility and scalability compared with previous approaches(4-6).

Plasmonic junctions with cucurbit[5]uril 'glue': fabrication of precise sub-nm junctions in gold nanoparticle assemblies

Aggregation of gold nanoparticles with rigid cucurbit[5]uril molecules generates fixed inter-particle separations of 0.91 nm. These nanoparticle assemblies possess discrete plasmonic modes which elucidate nanoscale growth and serve as molecular-recognition based SERS substrates.

Precise Subnanometer Plasmonic Junctions for SERS within Gold Nanoparticle Assemblies Using Cucurbit[n]uril "Glue"

Cucurbit[n]urils (CB[n]) are macrocyclic host molecules with subnanometer dimensions capable of binding to gold surfaces. Aggregation of gold nanoparticles with CB[n] produces a repeatable, fixed, and rigid interparticle separation of 0.9 nm, and thus such assemblies possess distinct and exquisitely sensitive plasmonics. Understanding the plasmonic evolution is key to their use as powerful SERS substrates. Furthermore, this unique spatial control permits fast nanoscale probing of the plasmonics of the aggregates "glued" together by CBs within different kinetic regimes using simultaneous extinction and SERS measurements. The kinetic rates determine the topology of the aggregates including the constituent structural motifs and allow the identification of discrete plasmon modes which are attributed to disordered chains of increasing lengths by theoretical simulations. The CBs directly report the near-field strength of the nanojunctions they create via their own SERS, allowing calibration of the enhancement. Owing to the unique barrel-shaped geometry of CB[n] and their ability to bind "guest" molecules, the aggregates afford a new type of in situ self-calibrated and reliable SERS substrate where molecules can be selectively trapped by the CB[n] and exposed to the nanojunction plasmonic field. Using this concept, a powerful molecular-recognition-based SERS assay is demonstrated by selective cucurbit[n]uril host-guest complexation.

One-step synthesis of ZnO nanosheets: a blue-white fluorophore

Zinc oxide is synthesised at low temperature (80A degrees C) in nanosheet geometry using a substrate-free, single-step, wet-chemical method and is found to act as a blue-white fluorophore. Investigation by atomic force microscopy, electron microscopy, and X-ray diffraction confirms zinc oxide material of nanosheet morphology where the individual nanosheets are polycrystalline in nature with the crystalline structure being of wurtzite character. Raman spectroscopy indicates the presence of various defects, while photoluminescence measurements show intense green (centre wavelength approximately 515 nm) blue (approximately 450 nm), and less dominant red (approximately 640 nm) emissions due to a variety of vacancy and interstitial defects, mostly associated with surfaces or grain boundaries. The resulting colour coordinate on the CIE-1931 standard is (0.23, 0.33), demonstrating potential for use as a blue-white fluorescent coating in conjunction with ultraviolet emitting LEDs. Although the defects are often treated as draw-backs of ZnO, here we demonstrate useful broadband visible fluorescence properties in as-prepared ZnO. 

Effect of the surface water layer on the optical signal in apertureless scanning near field optical microscopy

Optical signals measured in apertureless scanning near field optical microscopy (ASNOM) under ambient conditions are found to be affected significantly by the thin water layer absorbed on the surface under investigation, the presence of which is detected through measurements of the shear force experienced by the tip. This water layer also results in a large hysteresis between optical signals measured during approach and withdrawal of the tip to the sample surface. The role of this effect in ASNOM is anticipated to be significant, with the possibility of resultant topographically induced artefacts for ASNOM involving intermittent contact of tip and sample, but also providing a potential mechanism for nanoscale optical resolution.

Lorentz TEM investigation of the switching behavior in artificial spin ice building blocks

Frustration – the inability to simultaneously satisfy all interactions – occurs in a wide range of systems including neural networks, water ice and magnetic systems. An example of the latter is the so called spin-ice in pyrochlore materials [1] which have attracted a lot of interest not least due to the emergence of magnetic monopole defects when the ‘ice rules’ governing the local ordering breaks down [2]. However it is not possible to directly measure the frustrated property – the direction of the magnetic moments – in such spin ice systems with current experimental techniques. This problem can be solved by instead studying artificial spin-ice systems where the molecular magnetic moments are replaced by nanoscale ferromagnetic islands [3-8]. Two different arrangements of the ferromagnetic islands have been shown to exhibit spin ice behaviour: a square lattice maintaining four moments at each vertex [3,8] and the Kagome lattice which has only three moments per vertex but equivalent interactions between them [4-7]. Magnetic monopole defects have been observed in both types of lattices [7-8]. One of the challenges when studying these artificial spin-ice systems is that it is difficult to arrive at the fully demagnetised ground-state [6-8].
Here we present a study of the switching behaviour of building blocks of the Kagome lattice influenced by the termination of the lattice. Ferromagnetic islands of nominal size 1000 nm by 100 nm were fabricated in five island blocks using electron-beam lithography and lift-off techniques of evaporated 18 nm Permalloy (Ni80Fe20) films. Each block consists of a central island with four arms terminated by a different number and placement of ‘injection pads’, see Figure 1. The islands are single domain and magnetised along their long axis. The structures were grown on a 50 nm thick electron transparent silicon nitride membrane to allow TEM observation, which was back-coated with a 5 nm film of Au to prevent charge build-up during the TEM experiments.
To study the switching behaviour the sample was subjected to a magnetic field strong enough to magnetise all the blocks in one direction, see Figure 1. Each block obeys the Kagome lattice ‘ice-rules’ of “2-in, 1-out” or “1-in, 2-out” in this fully magnetised state. Fresnel mode Lorentz TEM images of the sample were then recorded as a magnetic field of increasing magnitude was applied in the opposite direction. While the Fresnel mode is normally used to image magnetic domain structures [9] for these types of samples it is possible to deduce the direction of the magnetisation from the Lorentz contrast [5]. All images were recorded at the same over-focus judged to give good Lorentz contrast.
The magnetisation was found to switch at different magnitudes of the applied field for nominally identical blocks. However, trends could still be identified: all the blocks with any injection pads, regardless of placement and number, switched the direction of the magnetisation of their central island at significantly smaller magnitudes of the applied magnetic field than the blocks without injection pads. It can therefore be concluded that the addition of an injection pad lowers the energy barrier to switching the connected island, acting as a nucleation site for monopole defects. In these five island blocks the defects immediately propagate through to the other side, but in a larger lattice the monopoles could potentially become trapped at a vertex and observed [10].
References

[1] M J Harris et al, Phys Rev Lett 79 (1997) p.2554.
[2] C Castelnovo, R Moessner and S L Sondhi, Nature 451 (2008) p. 42.
[3] R F Wang et al, Nature 439 (2006) 303.
[4] M Tanaka et al, Phys Rev B 73 (2006) 052411.
[5] Y Qi, T Brintlinger and J Cumings, Phys Rev B 77 (2008) 094418.
[6] E Mengotti et al, Phys Rev B 78 (2008) 144402.
[7] S Ladak et al, Nature Phys 6 (2010) 359.
[8] C Phatak et al, Phys Rev B 83 (2011) 174431.
[9] J N Chapman, J Phys D 17 (1984) 623.
[10] The authors gratefully acknowledge funding from the EPSRC under grant number EP/D063329/1.

Self-Similar Nested Flux Closure Structures in a Tetragonal Ferroelectric

In specific solid-state materials, under the right conditions, collections of magnetic dipoles are known to spontaneously form into a variety of rather complex geometrical patterns, exemplified by vortex and skyrmion structures. While theoretically, similar patterns should be expected to form from electrical dipoles, they have not been clearly observed to date: the need for continued experimental exploration is therefore clear. In this Letter we report the discovery of a rather complex domain arrangement that has spontaneously formed along the edges of a thin single crystal ferroelectric sheet, due to surface-related depolarizing fields. Polarization patterns are such that nanoscale “flux-closure” loops are nested within a larger mesoscale flux closure object. Despite the orders of magnitude differences in size, the geometric forms of the dual-scale flux closure entities are rather similar.

Shear instability of nanocrystalline silicon carbide during nanometric cutting

The shear instability of the nanoscrystalline 3C-SiC during nanometric cutting at a cutting speed of 100?m/s has been investigated using molecular dynamics simulation. The deviatoric stress in the cutting zone was found to cause sp3-sp2 disorder resulting in the local formation of SiC-graphene and Herzfeld-Mott transitions of 3C-SiC at much lower transition pressures than that required under pure compression. Besides explaining the ductility of SiC at 1500?K, this is a promising phenomenon in general nanoscale engineering of SiC. It shows that modifying the tetrahedral bonding of 3C-SiC, which would otherwise require sophisticated pressure cells, can be achieved more easily by introducing non-hydrostatic stress conditions.