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Microstructure Control and Iodine Doping of Bismuth Telluride


Heinz, Nicholas A. (2014) Microstructure Control and Iodine Doping of Bismuth Telluride. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/HKX2-QG08.


On the materials scale, thermoelectric efficiency is defined by the dimensionless figure of merit zT. This value is made up of three material components in the form zT = Tα2/ρκ, where α is the Seebeck coefficient, ρ is the electrical resistivity, and κ is the total thermal conductivity. Therefore, in order to improve zT would require the reduction of κ and ρ while increasing α. However due to the inter-relation of the electrical and thermal properties of materials, typical routes to thermoelectric enhancement come in one of two forms. The first is to isolate the electronic properties and increase α without negatively affecting ρ. Techniques like electron filtering, quantum confinement, and density of states distortions have been proposed to enhance the Seebeck coefficient in thermoelectric materials. However, it has been difficult to prove the efficacy of these techniques. More recently efforts to manipulate the band degeneracy in semiconductors has been explored as a means to enhance α.

The other route to thermoelectric enhancement is through minimizing the thermal conductivity, κ. More specifically, thermal conductivity can be broken into two parts, an electronic and lattice term, κe and κl respectively. From a functional materials standpoint, the reduction in lattice thermal conductivity should have a minimal effect on the electronic properties. Most routes incorporate techniques that focus on the reduction of the lattice thermal conductivity. The components that make up κl (κl = 1/3Cνl) are the heat capacity (C), phonon group velocity (ν), and phonon mean free path (l). Since the difficulty is extreme in altering the heat capacity and group velocity, the phonon mean free path is most often the source of reduction.

Past routes to decreasing the phonon mean free path has been by alloying and grain size reduction. However, in these techniques the electron mobility is often negatively affected because in alloying any perturbation to the periodic potential can cause additional adverse carrier scattering. Grain size reduction has been another successful route to enhancing zT because of the significant difference in electron and phonon mean free paths. However, grain size reduction is erratic in anisotropic materials due to the orientation dependent transport properties. However, microstructure formation in both equilibrium and nonequilibrium processing routines can be used to effectively reduce the phonon mean free path as a route to enhance the figure of merit.

This work starts with a discussion of several different deliberate microstructure varieties. Control of the morphology and finally structure size and spacing is discussed at length. Since the material example used throughout this thesis is anisotropic a short primer on zone melting is presented as an effective route to growing homogeneous and oriented polycrystalline material. The resulting microstructure formation and control is presented specifically in the case of In2Te3-Bi2Te3 composites and the transport properties pertinent to thermoelectric materials is presented. Finally, the transport and discussion of iodine doped Bi2Te3 is presented as a re-evaluation of the literature data and what is known today.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Microstructure, Thermoelectric, Bismuth telluride
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Materials Science
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Snyder, G. Jeffrey (advisor)
  • Haile, Sossina M. (co-advisor)
Thesis Committee:
  • Haile, Sossina M. (chair)
  • Schwab, Keith C.
  • Johnson, William Lewis
  • Snyder, G. Jeffrey
Defense Date:11 June 2014
Additional Information:Thesis title varies in 2014 Commencement program: Microstructure Control and Evaluation of Iodine Doping in Bismuth Telluride
Record Number:CaltechTHESIS:06112014-114312386
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8517
Deposited By: Nicholas Heinz
Deposited On:18 Jul 2014 16:58
Last Modified:04 Oct 2019 00:05

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