Kay Latham

Electrochemical Control of Photoluminescence in Two-Dimensional MoS2 Nanoflakes

Two-dimensional (2D) transition metal dichalcogenide semiconductors offer unique electronic and optical properties, which are significantly different from their bulk counterparts. It is known that the electronic structure of 2D MoS2, which is the most popular member of the family, depends on the number of layers. Its electronic structure alters dramatically at near atomically thin morphologies, producing strong photoluminescence (PL). Developing processes for controlling the 2D MoS2 PL is essential to efficiently harness many of its optical capabilities. So far, it has been shown that this PL can be electrically or mechanically gated. Here, we introduce an electrochemical approach to actively control the PL of liquid-phase-exfoliated 2D MoS2 nanoflakes by manipulating the amount of intercalated ions including Li(+), Na(+), and K(+) into and out of the 2D crystal structure. These ions are selected as they are crucial components in many bioprocesses. We show that this controlled intercalation allows for large PL modulations. The introduced electrochemically controlled PL will find significant applications in future chemical and bio-optical sensors as well as optical modulators/switches.

Near-infrared absorbing Cu12Sb4S13 and Cu3SbS4 nanocrystals: Synthesis, characterization, and photoelectrochemistry

Herein, we present the novel synthesis of tetrahedrite copper antimony sulfide (CAS) nanocrystals (Cu12Sb4S13), which display strong absorptions in the visible and NIR. Through ligand tuning, the size of the Cu12Sb4S13 NCs may be increased from 6 to 18 nm. Phase purity is achieved through optimizing the ligand chemistry and maximizing the reactivity of the antimony precursor. We provide a detailed investigation of the optical and photoelectrical properties of both tetrahedrite (Cu12Sb4S13) and famatinite (Cu3SbS4) NCs. These NCs were found to have very high absorption coefficients reaching 10(5) cm(-1) and band gaps of 1.7 and 1 eV for tetrahedrite and famatinite NCs, respectively. Ultraviolet photoelectron spectroscopy was employed to determine the band positions. In each case, the Fermi energies reside close to the valence band, indicative of a p-type semiconductor. Annealing of tetrahedrite CAS NC films in sulfur vapor at 350 °C was found to result in pure famatinite NC films, opening the possibility to tune the crystal structure within thin films of these NCs. Photoelectrochemistry of hydrazine free unannealed films displays a strong p-type photoresponse, with up to 0.1 mA/cm(2) measured under mild illumination. Collectively these optical properties make CAS NCs an excellent new candidate for both thin film and hybrid solar cells and as strong NIR absorbers in general.

High-Temperature Anodized WO3 Nanoplatelet Films for Photosensitive Devices

Anodization at elevated temperatures in nitric acid has been used for the production of highly porous and thick tungsten trioxide nanostructured films for photosensitive device applications. The anodization process resulted in platelet crystals with thicknesses of 20-60 nm and lengths of 100-1000 nm. Maximum thicknesses of approximately 2.4 microm were obtained after 4 h of anodization at 20 V. X-ray diffraction analysis revealed that the as-prepared anodized samples contain predominantly hydrated tungstite phases depending on voltage, while films annealed at 400 degrees C for 4 h are predominantly orthorhombic WO3 phase. Photocurrent measurements revealed that the current density of the 2.4 microm nanostructured anodized film was 6 times larger than the nonanodized films. Dye-sensitized solar cells developed using these films produced 0.33 V and 0.65 mA/cm2 in open- and short-circuit conditions.

Application of numerical basis sets to hydrogen bonded systems: A density functional theory study

We have investigated and compared the ability of numerical and Gaussian-type basis sets to accurately describe the geometries and binding energies of a selection of hydrogen bonded systems that are well studied theoretically and experimentally. The numerical basis sets produced accurate results for geometric parameters but tended to overestimate binding energies. However, a comparison of the time taken to optimize phosphinic acid dimer, the largest complex considered in this study, shows that calculations using numerical basis sets offer a definitive advantage where geometry optimization of large systems is required.

Anodization of Ti thin film deposited on ITO.

We have investigated several key aspects for the self-organization of nanotubes in RF sputtered titanium (Ti) thin films formed by the anodization process in fluoride-ion-containing neutral electrolytes. Ti films were deposited on indium tin oxide (ITO) glass substrates at room temperature and 300 degrees C, and then anodized. The films were studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis spectrometry before and after anodization. It was observed that anodization of high temperature deposited films resulted in nanotube type structures with diameters in the range of 10-45 nm for an applied voltage of 5-20 V. In addition, the anatase form of TiO(2) is formed during the anodization process which is also confirmed using photocurrent measurements. However, the anodization of room temperature deposited Ti films resulted in irregular pores or holes.

Electrowetting of superhydrophobic ZnO nanorods.

This paper reports the electrowetting properties of ZnO nanorods. These nanorods were grown on indium tin oxide (ITO) substrates using different liquid-phase deposition techniques and hydrophobized with sputtered Teflon. The surfaces display superhydrophobic properties. When the applied voltages are less than 35 V, the contact angle change is small and exhibits instant reversibility. For higher voltages, larger contact angle changes were observed. However, the surface was not reversible after removing the applied voltage and required mechanical agitation to return to its initial superhydrophobic state.

Sb2Te3 and Bi2Te3 based thermopower wave sources

Exothermic chemical reactions from nitrocellulose are coupled onto Sb2Te3 (antimony telluride) and Bi2Te3 (bismuth telluride) layers to generate self-propagating oscillating thermopower waves. P-type Sb2Te3 and N-type Bi2Te3 are employed due to their large Seebeck coefficients, high electrical conductivities and their complementary semiconducting properties. Sources based on both materials exhibit high power to mass ratios: up to 0.6 kW kg−1 for Sb2Te3 and 1.0 kW kg−1 for Bi2Te3. Having both P- and N-type semiconductors in the system, the combination of the outputs can be used for generating sources with polarities alternating in time.

Exfoliation Solvent Dependent Plasmon Resonances in Two-Dimensional Sub-Stoichiometric Molybdenum Oxide Nanoflakes.

Few-layer two-dimensional (2D) molybdenum oxide nanoflakes are exfoliated using a grinding assisted liquid phase sonication exfoliation method. The sonication process is carried out in five different mixtures of water with both aprotic and protic solvents. We found that surface energy and solubility of mixtures play important roles in changing the thickness, lateral dimension, and synthetic yield of the nanoflakes. We demonstrate an increase in proton intercalation in 2D nanoflakes upon simulated solar light exposure. This results in substoichiometric flakes and a subsequent enhancement in free electron concentrations, producing plasmon resonances. Two plasmon resonance peaks associated with the thickness and the lateral dimension axes are observable in the samples, in which the plasmonic peak positions could be tuned by the choice of the solvent in exfoliating 2D molybdenum oxide. The extinction coefficients of the plasmonic absorption bands of 2D molybdenum oxide nanoflakes in all samples are found to be high (ε > 10(9) L mol(-1) cm(-1)). It is expected that the tunable plasmon resonances of 2D molybdenum oxide nanoflakes presented in this work can be used in future electronic, optical, and sensing devices.

Novel copper materials based on the self-assembly of organophosphonic acids and bidentate amines

The hydrothermal synthesis and crystal structure of seven new supramolecular, heterocyclic adducts of copper organophosphonates are presented. Compounds 1–4, [CuX(D)2][C6H5P(O)(OH)2] [C6H5P(O)2(OH)], where D = 1,10-phenanthroline (phen) and X = Cl (1), Br (2), I (3), and NCS (4), are ionic in nature and possess a monoclinic structure, with the copper(II)-halide bond lying along a two-fold crystallographic axis. The crystals exhibit an alternating, lamellar structure in which 1-D ‘ribbons’ of [CuX(phen)2]+ cations are interleaved with 2-D ‘sheets’ of anionic [C6H5P(O)(OH)2][C6H5P(O)2(OH)]− dimers. The ribbons are associated through π–π bonding of the heterocyclic rings, and the acid sheets through a combination of π–π bonding of the aromatic rings, and hydrogen-bonding between the PO and P–OH of neighbouring acid dimers. Analogous derivatives have also been prepared by the reaction of [Cu(phen)2]Br with benzylphosphonic acid (5), [Cu(2,2′-bipy)2]I with phenylphosphonic acid (6) and [Cu(phen)2]I with phenylsulfonic acid (7). These complexes did not produce crystals suitable for single-crystal analysis. However, compounds (5) and (7) are thought to have similar structures to 1–4, whilst compound (6) has a different (2 : 2 : 3) ratio of copper : phosphonate : amine. Thus the supramolecular structure is robust for phenyl- and benzyl-phosphonic acids, with Cl, Br, I and NCS copper(II)phen complexes, and slightly varied by the presence of phenylsulfonic acid, but is not observed in the presence of 2,2′-bipy.

Interaction of hydrogen with ZnO nanopowders—evidence of hydroxyl group formation

There have been many investigations to reveal the nature of the hydrogen gas and ZnO nanopowder interaction at elevated temperatures, while at present no conclusive description of such an interaction has been confidently reported. In this work, we demonstrate that a hydroxyl group is formed during this interaction, depending on size and relative crystallinity of nanopowders. Our in situ Raman spectroscopy investigations show that the interaction directly affects the intensity of the Raman signal at 483 cm(-1), relative to the peak at 519 cm(-1). Ex situ x-ray diffraction (XRD) and infrared spectroscopy also show extra peaks at 44° and 1618 cm(-1), respectively, after hydrogenation. These peaks were all identified as surface hydroxyl groups, which can be related to the formation of water on the ZnO nanopowder surfaces.