etd@IISc Collection:
http://hdl.handle.net/2005/42
Wed, 24 Jan 2018 08:27:40 GMT2018-01-24T08:27:40ZStudy of Thermoelectric Properties of Lead Telluride Based Alloys and Two-Phase Compounds
http://hdl.handle.net/2005/2950
Title: Study of Thermoelectric Properties of Lead Telluride Based Alloys and Two-Phase Compounds
Authors: Bali, Ashoka
Abstract: The growing need of energy worldwide has lead to an increasing demand for alternative sources of power generation. Thermoelectric materials are one of the ‘green energy sources’ which convert directly heat into electricity, and vice–versa. The efficiency of this conversion is dependent on ‘figure of merit’ (z T), which depends on the material’s Seebeck coefficient (S), electrical resistivity (ρ) and thermal conductivity (κ) through the relation z T=S2T/ρκ, where T is the temperature. High values of z T lead to high efficiency, and therefore, z T must be maximized. Lead telluride is well–established thermoelectric material in the temperature range 350 K and 850 K. The aim of this thesis is to improve the z T of the material by adopting two different approaches – (i) doping/alloying and (ii) introducing additional interfaces in bulk i.e. having two phase PbTe.
In this thesis, first an introduction about the thermoelectric phenomenon is given, along with the material parameters on which z T depends. A survey of literature associated with PbTe is done and the current status of thermoelectric devices is summarized briefly. This is followed by a description of the synthesis procedure and the measurement techniques adopted in this work.
The first approach is the conventional alloying and doping of the material by which carrier concentration of the material is controlled so that maximum power factor Sρ2 is achieved and a simultaneous reduction of thermal conductivity takes place by mass fluctuation scattering. Under this, two systems have been studied. The first system is PbTe1−ySey alloys doped with In (nominal composition: Pb0.999In0.001Te1−ySey, y=0.01, 0.05, 0.10, 0.20, 0.25, 0.30). The compounds were single phase and polycrystalline. Lattice constants obtained from Rietveld refinement of X–ray diffraction (XRD) data showed that Vegard’s law was followed, indicating solid solution formation between PbTe and PbSe. Compositional analysis showed lower indium content than the nominal composition. Temperature dependent Seebeck coefficient showed all the samples to be n–type while Pisarenko plots showed that indium did not act as a resonant dopant. Electrical resistivity increased with temperature, while mobility vs T fitting showed a mixed scattering mechanism of acoustic phonon and ionized impurity scattering. Thermal conductivity followed a T1 dependence, which indicated acoustic phonon scattering. At high temperature, slight bipolar effect was observed, which showed the importance of control-ling carrier concentration for good thermoelectric properties. A z T of 0.66 was achieved at 800 K.
The second alloy studied under this approach was Mn doped Pb1−ySnyTe alloy (nominal composition Pb0.96−yMn0.04SnyTe (y=0.56, 0.64, 0.72, 0.80)). All the samples followed Vegard’s law, showing formation of complete solid solution between PbTe and SnTe. Microstructure analysis showed grain size distribution of <1 µm to more than 10 µm. Seebeck coefficient showed all samples were p-type and the role of two valence band conduction in p–type PbTe based materials. Electrical resistivity showed a de-crease possibly due to (i) large carrier concentration or (ii) increased mobility due to Mn2+ ions. Thermal conductivity decreased systematically with decreasing Sn content. Bipolar effect was observed at high temperatures. Accordingly, the highest z T of 0.82 at 720 K was obtained for the sample with Sn (y=0.56) content due to optimum carrier concentration and maximum disorder.
The second approach of having additional interfaces in bulk focuses on reducing thermal conductivity by scattering phonons. Under this approach, three systems were studied. The first system is PbTe with bismuth (Bi) secondary phase. The XRD and Ra-man studies showed that bismuth was not a dopant in PbTe, while micrographs showed micrometer–sized Bi secondary phase dispersed in bulk of PbTe. Reduction in Seebeck coeﬃcient showed possible hole donation across PbTe–Bi interfaces, while electrical re-sistivity and thermal conductivity showed that the role of electrons at the interfaces was more important than phonons for the present bismuth concentrations. For the parent PbTe, z T of 0.8 at 725 K was reached, which, however decreased for bismuth added samples.
The second system studied under the two phase approach was indium (In) added PbTe. Indium was not found to act as dopant in PbTe, while micrometer sized indium phase was found in PbTe bulk. A decrease in the electronic thermal conductivity ac-companied by a simultaneous increase of the electrical resistivity and Seebeck coeﬃcient throughout the measurement range indicated increased scattering of electrons at PbTe-In interfaces. Higher values of the lattice thermal conductivity showed that the PbTe–In interfaces were ineﬀective at scattering phonons, which was initially expected due to the lattice mismatch between PbTe and In. For PbTe with 3 at. % In phase, z T value of 0.78 at 723 K was achieved. Under the two phase approach, as a comparative study, PbTe with both micrometer sized Bi and In phases together was prepared, in which no improvement in z T was found.
A comparison of both the approaches showed that the alloying approach is better than the two–phase approach. This is because micrometer sized secondary phase scatter the electrons more than the phonons, leading to adverse eﬀect on the transport coef-ficients, and hence, on z T. Alloying, on the other hand, is more beneficial in reducing thermal conductivity by mass fluctuation scattering, along with a simultaneous reduction of electrical resistivity.Tue, 02 Jan 2018 18:30:00 GMThttp://hdl.handle.net/2005/29502018-01-02T18:30:00ZMulti-Nuclear and Multiple-Quantum NMR in the Solid-State : Methods and Applications
http://hdl.handle.net/2005/2951
Title: Multi-Nuclear and Multiple-Quantum NMR in the Solid-State : Methods and Applications
Authors: Jayasubba Reddy, Y
Abstract: NMR spectroscopy is a very powerful technique for the characterization of structure and dynamics of a variety of systems starting from small organic molecules to large biological macromolecules. In solids, the study of protons becomes more interesting because they are very sensitive to inter-molecular packing and are directly involved in hydrogen-bonding and aromatic π-π interactions, etc. The present thesis is devoted essentially to utilizing information from proton resonances obtained using multinuclear and multiple-quantum approaches. The thesis has two parts. The first part deals with methodological developments in the area of solid-state NMR, relevant to the study of rigid powder samples as well as partially ordered liquid crystalline materials. Methods have been proposed to investigate the structure of small molecules at moderate spinning frequencies and thermotropic liquid crystals at static conditions. Proton detected heteronuclear experimental methods based on both first and second-order cross polarization at moderate and ultra-fast magic angle spinning rates are also proposed. The second part of the thesis deals with the application of both newly proposed and existing solid state NMR methods to the study of several biologically relevant systems. These include the study of several designed as well as naturally occurring peptides. The use of first-principles calculations based on GIPAW method for supporting the experimentally obtained results has also been made. The thesis is divided into five chapters. In the second chapter, a new pulse sequence to correlate Double Quantum (DQ) proton frequencies to carbon Single Quantum (SQ) chemical shifts in the solid state has been proposed. In this sequence, named as MAS-J-1H (DQ)-13C-HMQC, the correlation between 1H and 13C is achieved through scalar coupling, while the double-quantum coherence among protons is generated through dipolar couplings. This experiment is particularly suited for the study of 13C in natural abundance. The advantages of the technique with applications to alanine, histidine and a model liquid crystalline material have been demonstrated. The assignment of 13C spectra of partially ordered systems has also been considered. In this case the assignment of the spectrum is a major challenge due to the interplay of anisotropic order and chemical shift parameters. The DQ-SQ correlation experiment described in the thesis has been applied to a well known liquid crystal and also to a novel thiophene based liquid crystal and the local order parameters of the liquid-crystal have been obtained.
The thesis also presents results on the azelaic acid -isonicotinamide co-crystal as well as the drug ibuprofen obtained by using novel methodologies. In the case of the former, the problem of overlap of resonances was overcome with the use of the REVERSE-CP approach to separate out the carbon attached protons from the rest of the protons. Subsequently, by the use of several combined approaches, the structural features were identified. A new heteronuclear correlation pulse sequence for solids under fast MAS conditions has also been tested. With low r.f powers, a second-order dipolar term mediated transfer of magnetization between I and S spin known as second order cross-polarization (SOCP) was exploited to obtain the entire spin system connectivity. Both carbon detected and proton detected experiments have been carried out and their utility evaluated. Similar approaches to shed light on the structure and conformation of a set of proline and pseudoproline based designed β-turn peptides that are used as templates for understanding protein folding have been made. Results of studies on two biologically important forms of the short-chain peptides namely glutathione reduced (GSH) and oxidized (GSSG) tripeptides are also presented.Tue, 02 Jan 2018 18:30:00 GMThttp://hdl.handle.net/2005/29512018-01-02T18:30:00ZElectrical Transport in the Hybrid Structures of 2D Van Der Waals Materials and Perovskite Oxide
http://hdl.handle.net/2005/2948
Title: Electrical Transport in the Hybrid Structures of 2D Van Der Waals Materials and Perovskite Oxide
Authors: Sahoo, Anindita
Abstract: Perovskite oxides have provided a wide variety of exotic functionalities based on their unique physical and chemical properties. By combining different perovskite oxides, interesting physical phenomena have been observed at the interfaces of perovskite heterostructures. The most interesting among these phenomena is the formation of two dimensional electron gas at the interface of two perovskite materials SrTiO3 and LaAlO3 which led to a number of fascinating physical properties such as metal-insulator transition, super-conductivity, large negative magnetoresistance and so on. This has raised the interest in exploiting the interface of various hybrids structures built on the perovskite oxide backbone. On the other hand, the two dimensional (2D) van der Waals materials such as graphene, MoS2, boron nitride etc. represent a new paradigm in the 2D electron-ics. The functionalities of these individual materials have been combined to obtain new enriched functionalities by stacking different materials together forming van der Waals heterostructures. In this work, we present a detailed study of the interface in hybrid structures made of vander Waals materials (graphene and MoS2) and their hybrids with a perovskite material namely, SrTiO3 which is known as the building block of complex oxide heterostructures.
In graphene-MoS2 vertical heterostructure, we have carried out a detailed set of investigations on the modulation of the Schottky barrier at the graphene-MoS2 interface with varying external electric field. By using different stacking sequences and device structures, we obtained high mobility at large current on-off ratio at room temperature along with a tunable Schottky barrier which can be varied as high as ∼ 0.4 eV by applying electric field. We also explored the interface of graphene and SrTiO3 as well as MoS2 and SrTiO3 by electrical transport and low frequency 1/f noise measurements. We observed a hysteretic feature in the transfer characteristics of dual gated graphene and MoS2 field effect transistors on SrTiO3. The dual gated geometry enabled us to measure the effective capacitance of SrTiO3 interface which showed an enhancement indicating the possible existence of negative capacitance developed by the surface dipoles at the interface of SrTiO3 and the graphene or MoS2 channel. Our 1/f noise study and the analysis of higher order statistics of noise also support the possibility of electric field-driven reorient able surface dipoles at the interface.Sun, 31 Dec 2017 18:30:00 GMThttp://hdl.handle.net/2005/29482017-12-31T18:30:00ZParticles and Fields in Superfluid Turbulence : Numerical and Theoretical Studies
http://hdl.handle.net/2005/2933
Title: Particles and Fields in Superfluid Turbulence : Numerical and Theoretical Studies
Authors: Shukla, Vishwanath
Abstract: In this thesis we study a variety of problems in superfluid turbulence, princi-pally in two dimensions. A summary of the main results of our studies is given below; we indicate the Chapters in which we present these.
In Chapter 1, we provide an overview of several problems in superfluid turbulence with special emphasis on background material for the problems we study in this thesis. In particular, we give: (a) a brief introduction of fluid turbulence; (b) an overview of superfluidity and the phenomenological two-fluid model; (c) a brief overview of experiments on superfluid turbulence; (d) an introductory accounts of the phenomenological models used in the study of superfluid turbulence. We end with a summary of the problems we study in subsequent Chapters of this thesis.
In Chapter 2, we present a systematic, direct numerical simulation of the two-dimensional, Fourier-truncated, Gross-Pitaevskii equation to study the turbulent evolutions of its solutions for a variety of initial conditions and a wide range of parameters. We find that the time evolution of this system can be classified into four regimes with qualitatively different statistical properties. First, there are transients that depend on the initial conditions. In the second regime, power- law scaling regions, in the energy and the occupation-number spectra, appear and start to develop; the exponents of these power laws and the extents of the scaling regions change with time and depend on the initial condition. In the third regime, the spectra drop rapidly for modes with wave numbers k > kc and partial thermalization takes place for modes with k < kc ; the self-truncation wave number kc(t) depends on the initial conditions and it grows either as a power of t or as log t. Finally, in the fourth regime, complete thermalization is achieved and, if we account for finite-size effects carefully, correlation functions and spectra are consistent with their nontrivial Berezinskii-Kosterlitz-Thouless forms. Our work is a natural generalization of recent studies of thermalization in the Euler and other hydrodynamical equations; it combines ideas from fluid dynamics and turbulence, on the one hand, and equilibrium and nonequilibrium statistical mechanics on the other.
In Chapter 3, we present the first calculation of the mutual-friction coefficients α and α (which are parameters in the Hall-Vinen-Bekharevich-Khalatnikov two-fluid model that we study in chapter 5) as a function of temperature in a homogeneous Bose gas in two-dimensions by using the Galerkin-truncated Gross-Pitaevskii equation, with very special initial conditions, which we obtain by using the advective, real, Ginzburg-Landau equation (ARGLE) and an equilibration procedure that uses a stochastic Ginzburg-Landau equation (SGLE). We also calculate the normal-fluid density as a function of temperature.
In Chapter 4, we elucidate the interplay of particles and fields in superfluids, in both simple and turbulent flows. We carry out extensive direct numerical simulations (DNSs) of this interplay for the two-dimensional (2D) Gross-Pitaevskii (GP) equation. We obtain the following results: (1) the motion of a particle can be chaotic even if the superfluid shows no sign of turbulence; (2) vortex motion depends sensitively on particle charateristics; (3) there is an effective, superfluid-mediated, attractive interaction between particles; (4) we introduce a short-range repulsion between particles, with range rSR, and study two- and many-particle collisions; in the case of two-particle, head-on collisions, we find that, at low values of rSR, the particle collisions are inelastic with coefficient of restitution e = 0; and, as we in-crease rSR, e becomes nonzero at a critical point, and finally attains values close to 1; (5) assemblies of particles and vortices show rich, turbulent, spatio-temporal evolution.
In Chapter 5, we present results from our direct numerical simulations (DNSs) of the Hall-Vinen-Bekharevich-Khalatnikov (HVBK) two-fluid model in two dimensions. We have designed these DNSs to study the statistical properties of inverse and forward cascades in the HVBK model. We obtain several interesting results that have not been anticipated hitherto: (1) Both normal-fluid and superfluid energy spectra, En(k) and Es(k), respectively, show inverse- and forward-cascade regimes; the former is characterized by a power law Es(k) En(k) kα whose exponent is consistent with α 5/3. (2) The forward-cascade power law depends on (a) the friction coefficient, as in 2D fluid turbulence, and, in addition, on (b) the coefficient B of mutual friction, which couples normal and superfluid compo-nents. (3) As B increases, the normal and superfluid velocities, un and us, re-spectively, get locked to each other, and, therefore, Es(k) En(k), especially in the inverse-cascade regime. (4) We quantify this locking tendency by calculating the probability distribution functions (PDFs) P(cos(θ)) and P(γ), where the angle θ ≡ (un • us)/( |un||us|) and the amplitude ratio γ = |un|/|us |; the former has a peak at cos(θ) = 1; and the latter exhibits a peak at γ = 1 and power-law tails on both sides of this peak. (4) This locking increases as we increase B, but the power-law exponents for the tails of P(γ) are universal, in so far as they do not depend on B, ρn/ρ, and the details of the energy-injection method. (5) We characterize the energy and enstrophy cascades by computing the energy and enstrophy fluxes and the mutual-friction transfer functions for all wave-number scales k.
In Chapter 6, we examine the multiscaling of structure functions in three-dimensional superfluid turbulence by using a shell-model for the three-dimensional HVBK equations. Our HVBK shell model is based on the GOY shell model. In particular, we examine the dependence of multiscaling on the normal-fluid fraction and the mutual-friction coefficients.
We hope our in silico studies of 2D and 3D superfluid turbulence will stimulate new experimental, numerical, and theoretical studies.Fri, 15 Dec 2017 18:30:00 GMThttp://hdl.handle.net/2005/29332017-12-15T18:30:00Z