Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy

The electronic structure of atomically precise armchair graphene nanoribbons of width N=7 (7-AGNRs) are investigated by scanning tunneling spectroscopy (STS) on Au(111). We record the standing waves in the local density of states of finite ribbons as a function of sample bias and extract the dispersion relation of frontier electronic states by Fourier transformation. The wave-vector-dependent contributions from these states agree with density functional theory calculations, thus enabling the unambiguous assignment of the states to the valence band, the conduction band, and the next empty band with effective masses of 0.41±0.08me,0.40±0.18me, and 0.20±0.03me, respectively. By comparing the extracted dispersion relation for the conduction band to corresponding height-dependent tunneling spectra, we find that the conduction band edge can be resolved only at small tip-sample separations and has not been observed before. As a result, we report a band gap of 2.37±0.06 eV for 7-AGNRs adsorbed on Au(111).

Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

Metal hexaborides with Sc, Ti or Mn

Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides con-firm previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms, show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directional and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest it may be possible to realize superconductivity in this compound if synthesized.

Nano-scale morphology and electron spectrum of defect states in low-k SiOCH films

Results of experimental investigations on the relationship between nanoscale morphology of carbon doped hydrogenated silicon-oxide (SiOCH) low-k films and their electron spectrum of defect states are presented. The SiOCH films have been deposited using trimethylsilane (3MS) - oxygen mixture in a 13.56 MHz plasma enhanced chemical vapor deposition (PECVD) system at variable RF power densities (from 1.3 to 2.6 W/cm2) and gas pressures of 3, 4, and 5 Torr. The atomic structure of the SiOCH films is a mixture of amorphous-nanocrystalline SiO2-like and SiC-like phases. Results of the FTIR spectroscopy and atomic force microscopy suggest that the volume fraction of the SiC-like phase increases from ∼0.2 to 0.4 with RF power. The average size of the nanoscale surface morphology elements of the SiO2-like matrix can be controlled by the RF power density and source gas flow rates. Electron density of the defect states N(E) of the SiOCH films has been investigated with the DLTS technique in the energy range up to 0.6 eV from the bottom of the conduction band. Distinct N(E) peaks at 0.25 - 0.35 eV and 0.42 - 0.52 eV below the conduction band bottom have been observed. The first N(E) peak is identified as originated from E1-like centers in the SiC-like phase. The volume density of the defects can vary from 1011 - 1017 cm-3 depending on specific conditions of the PECVD process.

Synthesis, characterization, and electronic structure studies of cubic Bi1.5ZnTa1.5O7 for photocatalytic applications

Bi1.5ZnTa1.5O7 (BZT) has been synthesized using an alkoxide based sol-gel reaction route. The evolution of the phases produced from the alkoxide precursors and their properties have been characterized as function of temperature using a combination of thermogravimetric analysis (TGA) coupled with mass spectrometry (MS), infrared emission spectrometry (IES), X-ray diffraction (XRD), ultraviolet and visible (UV-Vis) spectroscopy, Raman spectroscopy, and N2 adsorption/desorption isotherms. The lowest sintering temperature (600∘C) to obtain phase pure BZT powders with high surface area (14.5m2/g) has been determined from the thermal decomposition and phase analyses.The photocatalytic activity of the BZT powders has been tested for the decolorization of organic azo-dye and found to be photoactive under UV irradiation.The electronic band structure of the BZT has been investigated using density functional theory (DFT) calculations to determine the band gap energy (3.12 eV) and to compare it with experimental band gap (3.02 eV at 800∘C) from optical absorptionmeasurements. An excellent match is obtained for an assumption of Zn cation substitutions at specifically ordered sites in the BZT structure.

Energy band engineering of complex metal oxides

This doctoral studies focused on the development of new materials for efficient use of solar energy for environmental applications. The research investigated the engineering of the band gap of semiconductor materials to design and optimise visible-light-sensitive photocatalysts. Experimental studies have been combined with computational simulation in order to develop predictive tools for a systematic understanding and design on the crystal and energy band structures of multi-component metal oxides.

Resistance Noise in Electrically Biased Bilayer Graphene

We demonstrate that the low-frequency resistance uctuations, or noise, in bilayer graphene is strongly connected to its band structure, and displays a minimum when the gap between the conduction and valence band is zero. Using double-gated bilayer graphene devices we have tuned the zero gap and charge neutrality points independently, which oers a versatile mechanism to investigate the low-energy band structure, charge localization and screening properties of bilayer graphene.

Resistance Noise in Electrically Biased Bilayer Graphene

We demonstrate that the low-frequency resistance fluctuations, or noise, in bilayer graphene are strongly connected to its band structure and display a minimum when the gap between the conduction and valence band is zero. Using double-gated bilayer graphene devices we have tuned the zero gap and charge neutrality points independently, which offers a versatile mechanism to investigate the low-energy band structure, charge localization, and screening properties of bilayer graphene.

Theoretical description of time-resolved pump/probe photoemission in TaS2: a single-band DFT+DMFT(NRG) study within the quasiequilibrium approximation

In this work, we theoretically examine recent pump/probe photoemission experiments on the strongly correlated charge-density-wave insulator TaS2.We describe the general nonequilibrium many-body formulation of time-resolved photoemission in the sudden approximation, and then solve the problem using dynamical mean-field theory with the numerical renormalization group and a bare density of states calculated from density functional theory including the charge-density-wave distortion of the ion cores and spin-orbit coupling. We find a number of interesting results: (i) the bare band structure actually has more dispersion in the perpendicular direction than in the two-dimensional planes; (ii) the DMFT approach can produce upper and lower Hubbard bands that resemble those in the experiment, but the upper bands will overlap in energy with other higher energy bands; (iii) the effect of the finite width of the probe pulse is minimal on the shape of the photoemission spectra; and (iv) the quasiequilibrium approximation does not fully describe the behavior in this system.

Resistance Noise in Graphene Based Field Effect Devices

We present a low-frequency electrical noise measurement in graphene based field effect transistors. For single layer graphene (SLG), the resistance fluctuations is governed by the screening of the charge impurities by the mobile charges. However, in case of Bilayer graphene (BLG), the electrical noise is strongly connected to its band structure, and unlike single layer graphene, displays a minimum when the gap between the conduction and valence band is zero. Using double gated BLG devices we have tuned the zero gap and charge neutrality points independently, which offers a versatile mechanism to investigate the low-energy band structure, charge localization and screening properties of bilayer graphene

Intra-band electron pairing in the presence of a radiation field

A semiconductor with almost overlapping conduction bands b and c is considered. It is found that an attractive interaction leading to superconductivity can be induced between electrons in the conduction band b by a strong radiation field of monochromatic photons whose energy differs slightly from the band gap Ebc. The mechanism is the exchange of a photon and a phonon between the interacting electrons and the interaction is found to be proportional to the photon density.

Electronic structure and bonding of beta-rhombohedral boron using cluster fragment approach

Theoretical studies using density functional theory are carried out to understand the electronic structure and bonding and electronic properties of elemental beta-rhombohedral boron. The calculated band structure of ideal beta-rhombohedral boron (B-105) shows valence electron deficiency and depicts metallic behavior. This is in contrast to the experimental result that it is a semiconductor. To understand this ambiguity we discuss the electronic structure and bonding of this allotrope with cluster fragment approach using our recently proposed mno rule. This helps us to comprehend in greater detail the structure of B-105 and materials which are closely related to beta-rhombohedral boron. The molecular structures B12H12-2, B28H21+1, BeB27H21, LiB27H21-1, CB27H21+2, B57H36+3, Be3B54H36, and Li2CB54H36, and corresponding solids Li8Be3B102 and Li10CB102 are arrived at using these ideas and studied using first principles density functional theory calculations.

Influence of External Light Waves on the Thermoelectric Power Under Strong Magnetic Field in Ultrathin Films, Quantum Wires and Quantum Dots of Optoelectronic Materials

In this paper, an attempt is made to study the influence of external light waves on the thermoelectric power under strong magnetic field (TPSM) in ultrathin films (UFs), quantum wires (QWs) and quantum dots (QDs) of optoelectronic materials whose unperturbed dispersion relation of the conduction electrons are defined by three and two band models of Kane together with parabolic energy bands on the basis of newly formulated electron dispersion laws in each case. We have plotted the TPSM as functions of film thickness, electron concentration, light intensity and wavelength for UFs, QWs and ODs of InSb, GaAs, Hg1-xCdxTe and In1-xGaxAsyP1-y respectively. It appears from the figures that for UFs, the TPSM increases with increasing thickness in quantum steps, decreases with increasing electron degeneracy exhibiting entirely different types of oscillations and changes with both light intensity and wavelength and these two latter types of plots are the direct signature of light waves on opto-TPSM. For QWs, the opto-TPSM exhibits rectangular oscillations with increasing thickness and shows enhanced spiky oscillations with electron concentration per unit length. For QDs, the opto-TPSM increases with increasing film thickness exhibiting trapezoidal variations which occurs during quantum jumps and the length and breadth of the trapezoids are totally dependent on energy band constants. Under the condition of non-degeneracy, the results of opto-TPSM gets simplified into the well-known form of classical TPSM equation which the function of three constants only and being invariant of the signature of band structure.

Microscopic Mechanism of 1/f Noise in Graphene: Role of Energy Band Dispersion

A distinctive feature of single-layer graphene is the linearly dispersive energy bands, which in the case of multilayer graphene become parabolic. A simple electrical transport-based probe to differentiate between these two band structures will be immensely valuable, particularly when quantum Hall measurements are difficult, such as in chemically synthesized graphene nanoribbons. Here we show that the flicker noise, or the 1/f noise, in electrical resistance is a sensitive and robust probe to the band structure of graphene. At low temperatures, the dependence of noise magnitude on the carrier density was found to be opposite for the linear and parabolic bands. We explain our data with a comprehensive theoretical model that clarifies several puzzling issues concerning the microscopic origin of flicker noise in graphene field-effect transistors (GraFET).

Study of band offsets in InN/Ge heterojunctions

InN layers were directly grown on Ge substrate by plasma-assisted molecular beam epitaxy (PAMBE). The valence band offset (VBO) of wurtzite InN/Ge heterojunction is determined by X-ray photoemission spectroscopy (XPS). The valence band of Ge is found to be 0.18 +/- 0.04 eV above that of InN and a type-II heterojunction with a conduction band offset (CBO) of similar to 0.16 eV is found. The accurate determination of the VBO and CBO is important for the design of InN/Ge based electronic devices. (C) 2011 Elsevier B.A. All rights reserved.