David Hesp

Electronic and optical properties of single crystal SnS2: an earth-abundant disulfide photocatalyst

Tin disulfide is attractive as a potential visible-light photocatalyst because its elemental components are cheap, abundant and environmentally benign. As a 2-dimensional semiconductor, SnS2 can undergo exfoliation to form atomic layer sheets that provide high surface areas of photoactive material. In order to facilitate the deployment of this exciting material in industrial processes and electrolytic cells, single crystals of phase pure SnS2 are synthesised and analysed with modern spectroscopic techniques to ascertain the values of relevant semiconductor properties. An electron affinity of 4.16 eV, ionisation potential of 6.44 eV and work function of 4.81 eV are found. The temperature dependent band gap is also reported for this material for the first time. We confirm the valence band is formed predominately by a mixture S 3p and Sn 5s, while the conduction band consists of a mixture of Sn 5s and 5p orbitals and comment on the agreement between experiment and theory for values of band gaps.

Charge storage mechanism of activated manganese oxide composites for pseudocapacitors

Manganese oxides can undergo an electrochemical activation step that leads to greater capacitances, of which the structural change and mechanism remains poorly understood. Herein we present a wide-ranging study on a manganese oxide synthesised by annealing manganese(II) acetate precursor to 300 °C, which includes in operando monitoring of the structural evolution during the activation process via in situ Raman microscopy. Based on powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron and ex situ Raman microscopy, the as prepared manganese oxide was characterised as hausmannite-Mn3O4 with a minor portion of MnO2. The activation process of converting as-prepared hausmannite-Mn3O4 into amorphous MnO2 (with localised birnessite structure) by electrochemical cycling in 0.5 M Na2SO4 was examined. After activation, the activated MnOx exhibited capacitive performance of 174 F g−1 at a mass loading of 0.71 mg cm−2. The charge storage mechanism is proposed as the redox reaction between Mn(III) and Mn(IV) at outer surface active sites, since the disordered birnessite-MnO2 does not provide an ordered layer structure for cations and/or protons to intercalate.

Finite Size Effects in Magnetic and Optical Properties of Antiferromagnetic NiO Nanoparticles

We report systematic investigations on structural, magnetic and optical properties of NiO nanoparticles prepared by mechanical alloying. As-milled powders exhibit face centred cubic structure, but average particle size decreases and effective strain increases for the initial periods of milling. Lattice volume increases monotonically with a reduction in particle size. Antiferromagnetic NiO particles exhibit significant room temperature (RT) ferromagnetism with modest moment and coercivity. A maximum moment of 0.0147 μB/f.u at 12 kOe applied field and a coercivity of 160 Oe were obtained for 30 h milled NiO powder. Exchange bias decreases linearly with a decrease in NiO particle size. Thermo-magnetization data reveal the presence of mixed magnetic phases in milled powders and shifts magnetic phase transition towards high temperature with increasing milling. Annealing of milled NiO powder and photoluminescence studies show a large reduction in RT magnetic moment and blue-shifting of band edge emission peak. The observed properties are discussed on the basis of finite size effect, defect density, oxidation/reduction of Ni, increase in number of sublattices, uncompensated spins from surface to particle core, and interaction between uncompensated surfaces and particle core with lattice expansion.

Templated quasicrystalline molecular ordering.

Quasicrystals are materials with long-range ordering but no periodicity. We report scanning tunneling microscopy (STM) observations of quasicrystalline molecular layers on 5-fold quasicrystal surfaces. The molecules adopt positions and orientations on the surface consistent with the quasicrystalline ordering of the substrate. Carbon-60 adsorbs atop sufficiently separated Fe atoms on icosahedral Al-Cu-Fe to form a unique quasicrystalline lattice, whereas further C60 molecules decorate remaining surface Fe atoms in a quasi-degenerate fashion. Pentacene (Pn) adsorbs at 10-fold symmetric points around surface-bisected rhombic triacontahedral clusters in icosahedral Ag-In-Yb. These systems constitute the first demonstrations of quasicrystalline molecular ordering on a template.

Physical and electrical characterization of Mg-doped ZnO thin-film transistors

The effect of Mg-doping on the valence and conduction bands of ZnO grown at 200 °C using atomic layer deposition has been investigated using a range of physical characterization techniques: X-ray photoemission spectroscopy, inverse photoemission spectroscopy and spectrocopic ellipsometry. The conduction band minimum is seen to increase with Mg content hence confirming the increased band gap. The physical characterization has been linked with modeling of thin-film transistor structures whereby a defect state based model has been employed to explain the transport mechanisms within the film.

Scanning tunneling microscopy of a polygrain Al–Pd–Re quasicrystal: study of the relative surface stability

Scanning tunneling microscopy and x-ray photoemission spectroscopy on a polygrain icosahedral (i-) Al–Pd–Re quasicrystal (QC) show the formation of the twofold surfaces with symmetry and composition expected from the bulk. The predominant occurrence of the twofold surface on the polygrain i-QC having random grain orientation, as well as preferential formation of terrace edges, kinks and voids along the twofold axes, consistently indicates that the twofold surface, which has the highest atomic density, is the most stable among all the crystallographic planes.

Atomic-layer deposited thulium oxide as a passivation layer on germanium

A comprehensive study of atomic-layer deposited thulium oxide (Tm2O3) on germanium has been conducted using x-ray photoelectron spectroscopy (XPS), vacuum ultra-violet variable angle spectroscopic ...