Marcus C. Newton

Three-dimensional imaging of strain in a single ZnO nanorod

Nanoscale structures can be highly strained because of confinement effects and the strong influence of their external boundaries. This results in dramatically different electronic, magnetic and optical material properties of considerable utility. Third-generation synchrotron-based coherent X-ray diffraction has emerged as a non-destructive tool for three-dimensional (3D) imaging of strain and defects in crystals that are smaller than the coherence volume, typically a few cubic micrometres, of the available beams that have sufficient flux to reveal the materials structure. Until now, measurements have been possible only at a single Bragg point of a given crystal because of the limited ability to maintain alignment; it has therefore been possible to determine only one component of displacement and not the full strain tensor. Here we report key advances in our fabrication and experimental techniques, which have enabled diffraction patterns to be obtained from six Bragg reflections of the same ZnO nanocrystal for the first time. All three Cartesian components of the ion displacement field, and in turn the full nine-component strain tensor, have thereby been imaged in three dimensions.

ZnO tetrapod nanocrystals

ZnO has received considerable attention because of its unique optical, piezoelectric, and magnetic properties. It also readily self-assembles into a family of nanocrystalline structures. We review the current status of research into ZnO tetrapod nanocrystals. These crystals consist of a ZnO core in the zinc blende structure from which four ZnO arms in the wurtzite structure radiate. The arms are cylinders of hexagonal cross section, with each arm of equal length and diameter. Possible applications in optoelectronics, photovoltaics, spintronics, and piezoelectricity are discussed.

ZnO tetrapod Schottky photodiodes

The fabrication of an ultraviolet photodiode employing a single ZnO tetrapod nanocrystal is reported. This diode structure is prepared by depositing W and Pt electrodes to form Ohmic and Schottky contacts, respectively. Dark current-voltage measurements show rectifying behavior. The properties of the metal-semiconductor interface are studied with above and below band gap illumination. It is found that with increasing UV excitation the device converts from a rectifying to an Ohmic behavior. This effect is attributed to a flattening of the energy bands due to the migration of photogenerated carriers within the space charge region at the metal-semiconductor interface.

Zinc Oxide Nanostructures and High Electron Mobility Nanocomposite Thin Film Transistors

This paper reports on the synthesis of zinc oxide (ZnO) nanostructures and examines the performance of nanocomposite thin-film transistors (TFTs) fabricated using ZnO dispersed in both n- and p-type polymer host matrices. The ZnO nanostructures considered here comprise nanowires and tetrapods and were synthesized using vapor phase deposition techniques involving the carbothermal reduction of solid-phase zinc-containing compounds. Measurement results of nanocomposite TFTs based on dispersion of ZnO nanorods in an n-type organic semiconductor ([6, 6]-phenyl-C61-butyric acid methyl ester) show electron field-effect mobilities in the range 0.3-0.6 cm2 V-1s-1, representing an approximate enhancement by as much as a factor of 40 from the pristine state. The on/off current ratio of the nanocomposite TFTs approach 106 at saturation with off-currents on the order of 10 pA. The results presented here, although preliminary, show a highly promising enhancement for realization of high-performance solution-processable n-type organic TFTs.

Synthesis and characterisation of zinc oxide tetrapod nanocrystals

Zinc oxide is an important group II-VI semiconductor material with optical properties that permit stable emission at room temperature. We report on the synthesis of highly uniform nanocrystalline ZnO tetrapod (ZnO-T) nanostructures through a modified chemical vapour transport process. These self assembled nanocrystals are characterised by four cylindrical arms with a hexagonal facet all of which are joined at a tetrahedral core. Studies are carried out on ZnO tetrapods using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), photoluminescence spectroscopy (PLS) and Raman measurements. We find a simple technique to quench visible emission found in ZnO tetrapods as grown. We also observe Raman active modes suggesting that nitrogen is incorporated within our samples.

ZnO tetrapod p-n junction diodes

ZnO nanocrystals hold the potential for use in a wide range of applications particularly in optoelectronics. We report on the fabrication of a highly sensitive p-n junction diode structure based on a single ZnO tetrapod shaped nanocrystal. This device shows a noted response to ultraviolet light with high internal gain. The high reponsivities we have observed exceed 104 A/W and are likely due to impact-ionization effects at the p-n junction interface.

Photoresponse of ZnO Tetrapod Nanocrystal Schottky Diodes

The fabrication of an ultraviolet photodiode employing a single ZnO tetrapod nanocrystal is reported. We have attached two tungsten leads and one platinum lead to three of the arms of the tetrapod. By measuring the transport properties between each pair of leads we show that the tungsten contacts are ohmic and the platinum contacts are rectifying. Photoresponse measurements were carried out with above and below band gap illumination. We observe a much larger ultraviolet photoresponse for the rectifying Pt-ZnO-W junction than the linear W-ZnO-W junction. We conclude that the enhanced photoresponse of our rectifying junction results from a photoinduced reduction of the Schottky barrier height at the Pt-ZnO interface.

Time-Resolved Coherent Diffraction of Ultrafast Structural Dynamics in a Single Nanowire

The continuing effort to utilize the unique properties present in a number of strongly correlated transition metal oxides for novel device applications has led to intense study of their transitional phase state behavior. Here we report on time-resolved coherent X-ray diffraction measurements on a single vanadium dioxide nanocrystal undergoing a solid-solid phase transition, using the SACLA X-ray Free Electron Laser (XFEL) facility. We observe an ultrafast transition from monoclinic to tetragonal crystal structure in a single vanadium dioxide nanocrystal. Our findings demonstrate that the structural change occurs in a number of distinct stages attributed to differing expansion modes of vanadium atom pairs.

Ab initio molecular dynamics study of the structural and electronic transition in VO2

The temperature-induced structural and electronic transformation in VO2 between the monoclinic M1 and tetragonal rutile phases was studied by means of ab initio molecular dynamics, based on density functional theory with Hubbard correction (DFT+U). We compare the structure of both phases, transition temperature and atomic fluctuations both above and below the transition, as well as the phonon density of states and scattering intensity of centroid position, with experimental data. The good quantitative agreement indicates that the chosen DFT+U scheme is able to provide a fairly good description of the energetics of the system. Analysis of the dynamical processes associated with the structural transformation was carried out on the atomic scale by following the time evolution of dimerization amplitudes of vanadium atom chains and the twisting angle of vanadium dimers. The electronic transition was studied by tracing the changes in projected densities of states and their correlation with the evolution of the structural transformation. Our results reveal a strong interconnection between the structural and electronic transformations and show that they take place on the same time scale.

Coherent x-ray diffraction imaging of photo-induced structural changes in BiFeO3 nanocrystals

Multiferroic materials that exhibit coupling between ferroelectric and magnetic properties are of considerable utility for technological applications and are also interesting from a fundamental standpoint. When reduced to the nanoscale, multiferroic materials often display additional functionality that is dominated by interfacial and confinement effects. Bismuth ferrite (BiFeO3) is one such material with room temperature anti-ferromagnetic and ferroelectric ordering. Optical excitation of BiFeO3 crystals results in an elastic structural deformation of the lattice with a fast response on the pico-second time scale. Here we report on dynamic measurements to investigate the structural properties of BiFeO3 nanoscale crystals using laser excitation and three-dimensional Bragg coherent x-ray diffraction imaging. Tensile strain beyond 8 × 10^-2 was observed predominantly at the surface of the nanoscale crystal as evidenced in the reconstructed phase information and was correlated to photo-induced lattice deformation.