Strain Effects on Point Defects and Chain-Oxygen Order-Disorder Transition in 123-Structure Cuprate Superconductors

The energetics of Schottky defects in 123 cuprate superconductor series, $\rm REBa_2Cu_3O_7$ (where RE = lanthandies) and $\rm YAE_2Cu_3O_7$ (AE = alkali-earths), were found to have unusual relations if one considers only the volumetric strain. Our calculations reveal the effect of non-uniform changes of interatomic distances within the RE-123 structures, introduced by doping homovalent elements, on the Schottky defect formation energy. The energy of formation of Frenkel Pair defects, which is an elementary disordering event, in 123 compounds can be substantially altered under both stress and chemical doping. Scaling the oxygen-oxygen short-range repulsive parameter using the calculated formation energy of Frenkel pair defects, the transition temperature between orthorhombic and tetragonal phases is computed by quasi-chemical approximations (QCA). The theoretical results illustrate the same trend as the experimental measurements in that the larger the ionic radius of RE, the lower the orthorhombic/tetragonal phase transition temperature. This study provides strong evidence of the strain effects on order-disorder transition due to oxygens in the CuO chain sites.Comment: In print Phys Rev B (2004

Effects of Space Charge, Dopants, and Strain Fields on Surfaces and Grain Boundaries in YBCO Compounds

Statistical thermodynamical and kinetically-limited models are applied to study the origin and evolution of space charges and band-bending effects at low angle [001] tilt grain boundaries in YBa$_2$Cu$_3$O$_7$ and the effects of Ca doping upon them. Atomistic simulations, using shell models of interatomic forces, are used to calculate the energetics of various relevant point defects. The intrinsic space charge profiles at ideal surfaces are calculated for two limits of oxygen contents, i.e. YBa$_2$Cu$_3$O$_6$ and YBa$_2$Cu$_3$O$_7$. At one limit, O$_6$, the system is an insulator, while at O$_7$, a metal. This is analogous to the intrinsic and doping cases of semiconductors. The site selections for doping calcium and creating holes are also investigated by calculating the heat of solution. In a continuum treatment, the volume of formation of doping calcium at Y-sites is computed. It is then applied to study the segregation of calcium ions to grain boundaries in the Y-123 compound. The influences of the segregation of calcium ions on space charge profiles are finally studied to provide one guide for understanding the improvement of transport properties by doping calcium at grain boundaries in Y-123 compound.Comment: 13 pages, 5 figure

What limits supercurrents in high temperature superconductors? A microscopic model of cuprate grain boundaries

The interface properties of high-temperature cuprate superconductors have been of interest for many years, and play an essential role in Josephson junctions, superconducting cables, and microwave electronics. In particular, the maximum critical current achievable in high-Tc wires and tapes is well known to be limited by the presence of grain boundaries, regions of mismatch between crystallites with misoriented crystalline axes. In studies of single, artificially fabricated grain boundaries the striking observation has been made that the critical current Jc of a grain boundary junction depends exponentially on the misorientation angle. Until now microscopic understanding of this apparently universal behavior has been lacking. We present here the results of a microscopic evaluation based on a construction of fully 3D YBCO grain boundaries by molecular dynamics. With these structures, we calculate an effective tight-binding Hamiltonian for the d-wave superconductor with a grain boundary. The critical current is then shown to follow an exponential suppression with grain boundary angle. We identify the buildup of charge inhomogeneities as the dominant mechanism for the suppression of the supercurrent.Comment: 28 pages, 12 figure

C-axis lattice dynamics in Bi-based cuprate superconductors

We present results of a systematic study of the c axis lattice dynamics in single layer Bi2Sr2CuO6 (Bi2201), bilayer Bi2Sr2CaCu2O8 (Bi2212) and trilayer Bi2Sr2Ca2Cu3O10 (Bi2223) cuprate superconductors. Our study is based on both experimental data obtained by spectral ellipsometry on single crystals and theoretical calculations. The calculations are carried out within the framework of a classical shell model, which includes long-range Coulomb interactions and short-range interactions of the Buckingham form in a system of polarizable ions. Using the same set of the shell model parameters for Bi2201, Bi2212 and Bi2223, we calculate the frequencies of the Brillouin-zone center phonon modes of A2u symmetry and suggest the phonon mode eigenvector patterns. We achieve good agreement between the calculated A2u eigenfrequencies and the experimental values of the c axis TO phonon frequencies which allows us to make a reliable phonon mode assignment for all three Bi-based cuprate superconductors. We also present the results of our shell model calculations for the Gamma-point A1g symmetry modes in Bi2201, Bi2212 and Bi2223 and suggest an assignment that is based on the published experimental Raman spectra. The superconductivity-induced phonon anomalies recently observed in the c axis infrared and resonant Raman scattering spectra in trilayer Bi2223 are consistently explained with the suggested assignment.Comment: 29 pages, 13 figure

On the stability of 2 \sqrt{2} x 2 \sqrt{2} oxygen ordered superstructures in YBa2Cu3O6+x

We have compared the ground-state energy of several observed or proposed " 2 \sqrt{2} x 2 \sqrt{2} oxygen (O) ordered superstructures " (from now on HS), with those of "chain superstructures" (CS) (in which the O atoms of the basal plane are ordered in chains), for different compositions x in YBa2Cu3O6+x. The model Hamiltonian contains i) the Madelung energy, ii) a term linear in the difference between Cu and O hole occupancies which controls charge transfer, and iii) covalency effects based on known results for $t-J$ models in one and two dimensions. The optimum distribution of charge is determined minimizing the total energy, and depends on two parameters which are determined from known results for x=1 and x=0.5. We obtain that on the O lean side, only CS are stable, while for x=7/8, a HS with regularly spaced O vacancies added to the x=1 structure is more stable than the corresponding CS for the same x. We find that the detailed positions of the atoms in the structure, and long-range Coulomb interactions, are crucial for the electronic structure, the mechanism of charge transfer, the stability of the different phases, and the possibility of phase separation.Comment: 24 text pages, Latex, one fig. included as ps file, to be publisheb in Phys. Rev.

Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag2+ ion inside of a (AgCl6)4− complex as a result of the Jahn–Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron–nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn–Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra

Accelerated discovery of two crystal structure types in a complex inorganic phase field

The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large number of possible elemental compositions for such materials, and of the candidate structures at each composition1. For example, the discovery of inorganic extended solid structures has relied on knowledge of crystal chemistry coupled with time-consuming materials synthesis with systematically varied elemental ratios2,3. Computational methods have been developed to guide synthesis by predicting structures at specific compositions4,5,6 and predicting compositions for known crystal structures7,8, with notable successes9,10. However, the challenge of finding qualitatively new, experimentally realizable compounds, with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge8,11. Here we report the experimental discovery of two structure types by computational identification of the region of a complex inorganic phase field that contains them. This is achieved by computing probe structures that capture the chemical and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent experimental exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them

Orbital interactions and chemical reactivity of metal particles and metal surfaces

A review is presented with 101 refs. on chem. bonding to metal surfaces and small metal particles demonstrating the power of symmetry concepts to predict changes in chem. bonding. Ab-initio calcns. of chemisorption to small particles, as well as semiempirical extended Hueckel calcns. applied to the study of the reactivity of metal slabs are reviewed. On small metal particles, classical notions of electron promotion and hybridization are found to apply. The surroundings of a metal atom (ligands in complexes, other metal atoms at surfaces), affect bonding and reactivity through the prehybridization they induce. A factor specific for large particles and surfaces is the required localization of electrons on the atoms involved in the metal surface bond. At the surface, the bond energy is found to relate to the grou8p orbital local d. of states at the Fermi level. The use of this concept is extensively discussed and illustrated for chemisorption of CO and dissocn. of NO on metal surfaces. A discussion is given of the current decompn. schemes of bond energies and related concepts (exchange (Pauli)-repulsion, polarization, charge transfer). The role of non-orthogonality of fragment orbitals and of kinetic and potential energy for Pauli repulsion and (orbital) polarization is analyzed. Numerous examples are discussed to demonstrate the impact of those concepts on chem. bonding theor