Cage-size control of guest vibration and thermal conductivity in Sr8Ga16Si30-xGex

We present a systematic study of thermal conductivity, specific heat, electrical resistivity, thermopower and x-ray diffraction measurements performed on single-crystalline samples of the pseudoquaternary type-I clathrate system Sr8Ga16Si30-xGex, in the full range of 0 < x < 30. All the samples show metallic behavior with n-type majority carriers. However, the thermal conductivity and specific heat strongly depend on x. Upon increasing x from 0 to 30, the lattice parameter increases by 3%, from 10.446 to 10.726 A, and the localized vibrational energies of the Sr guest ions in the tetrakaidekahedron (dodecahedron) cages decrease from 59 (120) K to 35 (90) K. Furthermore, the lattice thermal conductivity at low temperatures is largely suppressed. In fact, a crystalline peak found at 15 K for x = 0 gradually decreases and disappears for x > 20, evolving into the anomalous glass-like behavior observed for x = 30. It is found that the increase of the free space for the Sr guest motion directly correlates with a continuous transition from on-center harmonic vibration to off-center anharmonic vibration, with consequent increase in the coupling strength between the guest's low-energy modes and the cage's acoustic phonon modes.Comment: 7 pages, 7 figures, submitted to PR

Glass-Like Heat Conduction in High-Mobility Crystalline Semiconductors

The thermal conductivity of polycrystalline semiconductors with type-I clathrate hydrate crystal structure is reported. Ge clathrates (doped with Sr and/or Eu) exhibit lattice thermal conductivities typical of amorphous materials. Remarkably, this behavior occurs in spite of the well-defined crystalline structure and relatively high electron mobility ($\sim 100 cm^2/Vs$). The dynamics of dopant ions and their interaction with the polyhedral cages of the structure are a likely source of the strong phonon scattering.Comment: 4 pages, 3 postscript figures, to be published, Phys. Rev. Let

Resonant States in the Electronic Structure of the High Performance Thermoelectrics AgPbmSbTe_{m}SbTe_{2+m}$ ; The Role of Ag-Sb Microstructures

Ab initio electronic structure calculations based on gradient corrected density functional theory were performed on a class of novel quaternary compounds AgPb$_{m}SbTe$_{2+m}$, which were found to be excellent high temperature thermoelctrics with large figure of merit ZT ~2.2 at 800K. We find that resonant states appear near the top of the valence and bottom of the conduction bands of bulk PbTe when Ag and Sb replace Pb. These states can be understood in terms of modified Te-Ag(Sb) bonds. Electronic structure near the gap depends sensitively on the microstructural arrangements of Ag-Sb atoms, suggesting that large ZT values may originate from the nature of these ordering arrangements.Comment: Accepted in Physical Review Letter

Glasslike vs. crystalline thermal conductivity in carrier-tuned Ba8Ga16X30 clathrates (X = Ge, Sn)

The present controversy over the origin of glasslike thermal conductivity observed in certain crystalline materials is addressed by studies on single-crystal x-ray diffraction, thermal conductivity k(T) and specific heat Cp(T) of carrier-tuned Ba8Ga16X30 (X = Ge, Sn) clathrates. These crystals show radically different low-temperature k(T) behaviors depending on whether their charge carriers are electrons or holes, displaying the usual crystalline peak in the former case and an anomalous glasslike plateau in the latter. In contrast, Cp(T) above 4 K and the general structural properties are essentially insensitive to carrier tuning. We analyze these combined results within the framework of a Tunneling/Resonant/Rayleigh scatterings model, and conclude that the evolution from crystalline to glasslike k(T) is accompanied by an increase both in the effective density of tunnelling states and in the resonant scattering level, while neither one of these contributions can solely account for the observed changes in the full temperature range. This suggests that the most relevant factor which determines crystalline or glasslike behavior is the coupling strength between the guest vibrational modes and the frameworks with different charge carriers.Comment: 8 pages, 4 figures, 4 tables, submitted to Phys. Rev.

Thermoelectric transport of perfectly conducting channels in two- and three-dimensional topological insulators

Topological insulators have gapless edge/surface states with novel transport properties. Among these, there are two classes of perfectly conducting channels which are free from backscattering: the edge states of two-dimensional topological insulators and the one-dimensional states localized on dislocations of certain three-dimensional topological insulators. We show how these novel states affect thermoelectric properties of the systems and discuss possibilities to improve the thermoelectric figure of merit using these materials with perfectly conducting channels.Comment: 10 pages, 6 figures, proceedings for The 19th International Conference on the Application of High Magnetic Fields in Semiconductor Physics and Nanotechnology (HMF-19

Lattice thermal conductivity of disordered NiPd and NiPt alloys

Numerical calculations of lattice thermal conductivity are reported for the binary alloys NiPd and NiPt. The present work is a continuation of an earlier paper by us [PRB, 72, 214207 (2005)]which had developed a theoretical framework for the calculation of configuration-averaged lattice thermal conductivity and thermal diffusivity in disordered alloys. The formulation was based on the augmented space theorem combined with a scattering diagram technique. In this paper we shall show dependence of the lattice thermal conductivity on a series of variables like phonon frequency, temperature and alloy composition. The temperature dependence of $\kappa(T)$ and its realtion to the measured thermal conductivity is discussed. The concentration dependence of $\kappa$ appears to justify the notion of a minimum thermal conductivity as discussed by Kittel, Slack and others. We also study the frequency and composition dependence of the thermal diffusivity averaged over modes. A numerical estimate of this quantity gives an idea about the location of mobility edge and the fraction of states in the frequency spectrum which is delocalized.Comment: 23 pages, 18 figure

Towards a generalized computational fluid dynamics technique for all Mach numbers

Currently there exists no single unified approach for efficiently and accurately solving computational fluid dynamics (CFD) problems across the Mach number regime, from truly low speed incompressible flows to hypersonic speeds. There are several CFD codes that have evolved into sophisticated prediction tools with a wide variety of features including multiblock capabilities, generalized chemistry and thermodynamics models among other features. However, as these codes evolve, the demand placed on the end user also increases simply because of the myriad of features that are incorporated into these codes. In order for a user to be able to solve a wide range of problems, several codes may be needed requiring the user to be familiar with the intricacies of each code and their rather complicated input files. Moreover, the cost of training users and maintaining several codes becomes prohibitive. The objective of the current work is to extend the compressible, characteristic-based, thermochemical nonequilibrium Navier-Stokes code GASP to very low speed flows and simultaneously improve convergence at all speeds. Before this work began, the practical speed range of GASP was Mach numbers on the order of 0.1 and higher. In addition, a number of new techniques have been developed for more accurate physical and numerical modeling. The primary focus has been on the development of optimal preconditioning techniques for the Euler and the Navier-Stokes equations with general finite-rate chemistry models and both equilibrium and nonequilibrium thermodynamics models. We began with the work of Van Leer, Lee, and Roe for inviscid, one-dimensional perfect gases and extended their approach to include three-dimensional reacting flows. The basic steps required to accomplish this task were a transformation to stream-aligned coordinates, the formulation of the preconditioning matrix, incorporation into both explicit and implicit temporal integration schemes, and modification of the numerical flux formulae. In addition, we improved the convergence rate of the implicit time integration schemes in GASP through the use of inner iteration strategies and the use of the GMRES (General Minimized Resisual) which belongs to the class of algorithms referred to as Krylov subspace iteration. Finally, we significantly improved the practical utility of GASP through the addition of mesh sequencing, a technique in which computations begin on a coarse grid and get interpolated onto successively finer grids. The fluid dynamic problems of interest to the propulsion community involve complex flow physics spanning different velocity regimes and possibly involving chemical reactions. This class of problems results in widely disparate time scales causing numerical stiffness. Even in the absence of chemical reactions, eigenvalue stiffness manifests itself at transonic and very low speed flows which can be quantified by the large condition number of the system and evidenced by slow convergence rates. This results in the need for thorough numerical analysis and subsequent implementation of sophisticated numerical techniques for these difficult yet practical problems. As a result of this work, we have been able to extend the range of applicability of compressible codes to very low speed inviscid flows (M = .001) and reacting flows

Thermoelectric transport in strained Si and Si/Ge heterostructures

The anisotropic thermoelectric transport properties of bulk silicon strained in [111]-direction were studied by detailed first-principles calculations focussing on a possible enhancement of the power factor. Electron as well as hole doping were examined in a broad doping and temperature range. At low temperature and low doping an enhancement of the power factor was obtained for compressive and tensile strain in the electron-doped case and for compressive strain in the hole-doped case. For the thermoelectrically more important high temperature and high doping regime a slight enhancement of the power factor was only found under small compressive strain with the power factor overall being robust against applied strain. To extend our findings the anisotropic thermoelectric transport of an [111]-oriented Si/Ge superlattice was investigated. Here, the cross-plane power factor under hole-doping was drastically suppressed due to quantum-well effects, while under electron-doping an enhanced power factor was found. With that, we state a figure of merit of ZT$=0.2$ and ZT$=1.4$ at T=\unit[300]{K} and T=\unit[900]{K} for the electron-doped [111]-oriented Si/Ge superlattice. All results are discussed in terms of band structure features

Collaboration and teamwork: immersion and presence in an online learning environment

In the world of OTIS, an online Internet School for occupational therapists, students from four European countries were encouraged to work collaboratively through problem-based learning by interacting with each other in a virtual semi-immersive environment. This paper describes, often in their own words, the experience of European occupational therapy students working together across national and cultural boundaries. Collaboration and teamwork were facilitated exclusively through an online environment, since the students never met each other physically during the OTIS pilot course. The aim of the paper is to explore the observations that here was little interaction between students from different tutorial groups and virtual teamwork developed in each of the cross-cultural tutorial groups. Synchronous data from the students was captured during tutorial sessions and peer-booked meetings and analysed using the qualitative constructs of ‘immersion’, ‘presence’ and ‘reflection in learning’. The findings indicate that ‘immersion’ was experienced only to a certain extent. However, both ‘presence’ and shared presence were found by the students, within their tutorial groups, to help collaboration and teamwork. Other evidence suggests that communities of interest were established. Further study is proposed to support group work in an online learning environment. It is possible to conclude that collaborative systems can be designed, which encourage students to build trust and teamwork in a cross cultural online learning environment.</p