The thesis entitled "Layered Oxides and Phosphates of Bismuth: New Structural Types and Related Properties" consists of three parts and six chapters. It begins with an introductory note providing a brief overview of the existing literature on bismuth based layered oxides. Part A of the thesis describes novel variants of the Aurivillius, Scheelite and Fluorite related phases with special emphasis on photocatalytic behavior of these materials. Chapter 1 describes two new compounds, LiBi4Nb3O14 and LiBi4Ta3O14 characterized by single crystal X-ray diffraction to depict a unique structure, which have similarities with both an ideal Aurivillius phase and a typical hexagonal tungsten bronze. Photo-degradation of a wide range of water pollutants, which include commonly, used dyes in textile industry and phenols suggest selectivity of LiBi4Nb3O14 towards hydroxyl group containing aromatic compounds. Chapter 2, Section 1 presents the structure of BaBi2Mo4O16 as a new compound among Scheelites, which shows high selectivity towards photo-degradation of non- chloro-containing aromatic systems. Further, the degradation rates are found to be significantly higher than the commercial TiO2 catalyst for nitro and methyl phenols. The solid solution, BaBi2Mo4-xWxO16 (0.25 ≤ x ≤ 1) has been analyzed to obtain insights into the compositional aspects. Section 2 has a detailed discussion on the structural stability of the Scheelite BaBi2Mo4O16 upon substitution of divalent cations, Ca, Sr and Pb at the barium site. The potential of these compounds as photocatalytic materials has been investigated. Chapter 3 describes a detailed kinetic analysis along with a single crystal X-ray structure determination of Ba2Bi24Mo10O68. Substitution at the Bi site by Ba and La results in differences in photocatalytic activity. All variants are observed to show specificity towards nitro- substitution at the ortho- position in phenols. Chapter 4 is a re-determination of the crystal structures of the triclinic polymorphs of BiNbO4 and BiTaO4 since one of the earlier reports is on a twinned crystal with large, unacceptable thermal ellipsoids and the other is a powder data -based Rietveld refinement of this model. Further BiNbO4 has been investigated to evaluate selectivity in photo degradation of dyes. In Part B, an attempt to correlate the crystal structure with relaxor ferroelectric behavior is outlined. Chapter 5 investigates a bismuth based tetratungsten bronze (TTB) relaxor material for the first time. Single crystal X-ray diffraction studies on the composition, x = 0.77 of the solid solution, Ba5x/2Bi(1-x)5/3Nb5O15 (0.52 ≤ x ≤ 0.8) depicts disorder in the occupancies of barium and bismuth atoms which is suggested to be the possible origin for relaxor behavior. Dielectric measurements correlate the structural features. Part C consists of a structure-based analysis on possible correlations with ionic conductivity. Chapter 6 describes two new crystal structures, Bi17P8O45.5 and Bi20P8O50, and the evolution of the series, Bi16+xP8O45+(3x-2)/2 (0.7 ≤ x ≤ 4.0). A rationale for the low ionic conductivity exhibited in these materials is arrived at from the arrangement of atoms in the crystal structure. Appendix A consists of a description of the crystal structure and ionic conductivity of Bi3W2O10.5.

 Molecular Beam Epitaxy is an advanced method for the synthesis of single-crystal thin-film structures. However, the growth behavior varies case by case due to the complicated kinetic process. In this thesis, the epitaxial growth processes of AlxIn1-xN alloy and Bi2Se3 thin-films are studied. Heteroepitaxial growth of AlxIn1-xN alloy on GaN(0001) substrate is carried out in the Nitrogen-rich flux conditions. A series of transient growth stages are identified from the initiation of the deposition. A significant effect of source beam-flux on the incorporation rate of Indium atoms is observed and measured. A correlation between the incorporation rate and the growth conditions (flux ratio and growth temperature) is revealed by the dependence of the growth-rate of the film on beam fluxes. A mathematic model is then suggested to explain the effect, through which the measured results indicating a surface diffusing and trapping process is indicated. Unexpected behavior of the lattice-parameter evolution of the growth front during deposition is also observed, indicating a complex strain-relaxation process of the epilayers. For three-dimensional (3D) topological insulator of Bi2Se3, growths are attempted on various substrate surfaces, including clean Si(111)-(7x7), Hydrogen terminated Si(111), Bismuth induced Si(111) reconstructed surfaces, GaN(0001), and some selenide “psudo-substrates”. The specific formation process of this quintuple-layered material in MBE is investigated, from which the Van der Waals epitaxy growth characteristics inherent to deposition of Bi2Se3 is determined, and the mechanism of the “two-step growth” technique for this material is further clarified. Among the various substrates, those that are inert to chemical reaction with Bi/Se are important for the growth. The epilayers’ lattice-misfit with the substrate is also a crucial factor to the structural quality of the Bi2Se3 epifilms, such as the defects density and the single-crystalline domain size. The effect of a vicinal substrate on suppressing the twin-defects in film is also addressed. Using a suitable substrate and adapting an optimal condition, ultra-thin films of Bi2Se3 with a superior structural quality have been achieved. Multilayered Bi2Se3 structures with ZnSe and In2Se3 spacers are attempted. Finally the high-quality superlattices of Bi2Se3/In2Se3 are successfully synthesized. The hetero-interfaces in the superlattice structure of Bi2Se3/In2Se3 are sharp, and the individual layers are uniform with thicknesses being strictly controlled. The behaviors of strain evolution during the hetero-growth process are finally investigated. An exponential relaxation of misfit strain is observed. And the correlation between the residual strain and the starting surface in the initial growth stage is also identified. / published_or_final_version / Physics / Doctoral / Doctor of Philosophy

abstract / Physics / Doctoral / Doctor of Philosophy

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A method of performing accurate oxygen analysis on cuprate based superconducting materials was established using electron probe micro analysis (EPMA). A range of YBa₂Cu₃O_δ ceramics with varying oxygen concentration were used to test the method. Using YBCO as a reference material, a suitable standard for oxygen analysis of Bi₂Sr₂CaCu₂O_δ (BiSCCO-2212) materials was obtained. This standard was used to perform full elemental analysis of a range of BiSCCO-2212 crystals, post annealed in pO₂'s between 10^-5-2atm. When the average Cu valence of each crystal was calculated and plotted as a function of the critical temperature (T_c) for each crystal, it was shown that BiSCCO-2212 materials conformed to the 'universal' trend illustrated by most other HTS and did not exhibit anomalous behaviour as had been previously believed. The phase assemblage and superconducting properties of BiSCCO-2212 Ag-clad multifilamental wires, prepared using the powder-in-tube (PIT) method by BICC, were studied as a function of a time/temperature profile. pO₂ of the processing atmosphere was found to be the predominant factor in determining the stoichiometry of the 2212 phase within wires. The phase assemblage is not simply a function of pO₂ as previously believed and can be controlled, in part, by the post annealing temperature. Homogenisation of the phase assemblage in BiSCCO-2212 Ag-clad wires can be achieved by prolonged heating (96hrs) at an appropriate temperature. An investigation into the 10K superconducting BiSCCO phase has shown the Sr-rich solid solution to extend towards the ideal stoichiometry of 2:2:1 (Bi:Sr:Cu) with increasing pO₂. Using a combination of high pO₂ (60atm) to achieve the appropriate Bi:Sr stoichiometry followed by post annealing in N₂ to adjust the oxygen content, it was possible to prepare single-phase ceramics of stoichiometry Bi_2.11(2)Sr_1.90(2)Cu_0.99(2)O_δ with a T_c=10.5K(5).

Using time-resolved photo-induced reflectivity, we reported for the first time a systematic work on the ultrafast response of Bi₂Sr₂CaCu₂O_8+δ (BSCCO-2212) and Tl₂Ba₂CuO_6+δ (TBCO-2201), measurements of detwinned YBa₂Cu₃O_7-δ (YBCO-123) single crystal with the electric field ̲E parallel to the a and b-axis and high-resolution measurements of the rising edge dynamics of YBCO-123 thin films. We identified similar photo-induced responses for BSCCO, TBCO and for YBCO with ̲E ⊥ ̲b, which indicates that we observed a universal response of HTSC coming from the CuO2 superconducting planes. This latter dynamics is composed of three different components corresponding to the superconducting, pseudogap and normal state. A bi-molecular model has been put forward to explain the linear temperature dependence of the decay rate; the model implies that the re-formation of the condensate is limited by the rate at which quasiparticle interact. Moreover, we observed superconducting fluctuations up to 13K above T_c and a divergence of the long-lived component magnitude at very low temperature, which is explained by a cw heating model. In the pseudogap state, we have several indications that the negative peak observed between T_c and T* has a different origin from that of the superconducting signal below T_c. We argued that the probe mechanism of the pseudogap signal is electronic excitations of the pseudogap correlations. In the normal state, the observed dynamics is similar to that of simple metals. In the second part of this thesis, the rising edge dynamics of YBCO has been resolved in time. The model developed to interpret the results implies that the hot quasiparticles relaxation time down to the Fermi energy is 55fs. In this context, we proved that the Mazin model cannot explain both the oscillatory and the non-oscillatory part of the dynamics in YBCO. Finally, in YBCO-123, a new response has been observed with ̲E ∥ ̲b. We argued that the origin of this component is intraband transitions. This dynamics is solely responsive to the pseudogap, coming from the difference in scattering rate between pre-formed pairs and quasiparticles in the Drude reflectivity. The response with ̲E ⊥ ̲b exhibits a strong a-b plane anisotropy in its long-lived component, which can be interpreted as a d-wave gap symmetry using the thermally-activated model.

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