Abstract

The Electrodeposition of PbTe Nanowires for Thermoelectric Applications

by

Peter Hillman

Doctor of Philosophy in Chemistry

University of California, Berkeley

Professor Angelica Stacy, Chair

The electrodeposition of PbTe nanowires for thermoelectric applications is presented in this thesis. The Pb-Te electrochemical system was investigated to determine the optimal conditions for deposition. It was found that citric acid complexed tellurium in solution shifting its reduction potential cathodically. The shift in reduction potential led to the deposition of pure PbTe without any observable excess tellurium.

Nanowires of PbTe were doped p-type and n-type through the addition of thallium and indium to the plating solution. Indium-doped nanowire arrays showed a linear relation between lattice parameter and atomic percent indium confirming successful incorporation. The lattice parameter trend in thallium-doped nanowire arrays was linear only after annealing. In the case of thallium doping, thallium tellurides were formed, which upon annealing formed a solid solution with PbTe.

The results of the thallium doping study led to the investigation of the Tl-Te electrochemical system. Cyclic voltammagrams were used to determine the deposition mechanism of TlTe and Tl5Te3. Thin films and nanowire arrays of these compounds were deposited. This was the first study of the electrochemical Tl-Te system and the first report of the electrodeposition of TlTe and Tl5Te3.

Thermoelectric measurements were conducted on thin films and nanowire arrays of PbTe. The Seebeck coefficient and resistivity of PbTe thin film were measured. Results from thin films were complicated by the Pt substrate on which PbTe was deposited. Subtracting the effects of the Pt layer suggested PbTe thin films could have a large zT, however further work is needed to confirm this result. Resistivity measurements on nanowire arrays were also conducted. Despite efforts to minimize the oxidation of PbTe nanowires, good electrical contacts could not be created. The resistivity of nanowire arrays were orders of magnitude higher than expected. As a result of their low conductivity, the thermoelectric efficiency of PbTe nanowires were negliglable.

Nanotube arrays of conductive polyaniline were synthesized through the electrochemical deposition into porous anodic alumina. PbTe nanowires were deposited into these nanotubes to create a PbTe/polyaniline core-shell structure. PbTe/polyaniline hybrids should have a lower thermal conductivity than pure PbTe. Measurements of PbTe/polyaniline core-shell nanowires are still needed to confirm the predicted lower thermal conductivity.