Janakiraman Balachandran

Effect of Length and Contact Chemistry on the Electronic Structure and Thermoelectric Properties of Molecular Junctions

We present a combined experimental and computational study that probes the thermoelectric and electrical transport properties of molecular junctions. Experiments were performed on junctions created by trapping aromatic molecules between gold electrodes. The end groups (-SH, -NC) of the aromatic molecules were systematically varied to study the effect of contact coupling strength and contact chemistry. When the coupling of the molecule with one of the electrodes was reduced by switching the terminal chemistry from -SH to -H, the electrical conductance of molecular junctions decreased by an order of magnitude, whereas the thermopower varied by only a few percent. This has been predicted computationally in the past and is experimentally demonstrated for the first time. Further, our experiments and computational modeling indicate the prospect of tuning thermoelectric properties at the molecular scale. In particular, the thiol-terminated aromatic molecular junctions revealed a positive thermopower that increased linearly with length. This positive thermopower is associated with charge transport primarily through the highest occupied molecular orbital, as shown by our computational results. In contrast, a negative thermopower was observed for a corresponding molecular junction terminated by an isocyanide group due to charge transport primarily through the lowest unoccupied molecular orbital.

Length dependence of frontier orbital alignment in aromatic molecular junctions

We report on experiments and computations performed on a series of aromatic monothiol molecular junctions (AMMJs) to ascertain both the identity of the frontier molecular orbitals (FMOs) and their approximate energetic separation from the chemical potential. Joint transition voltage spectroscopy and thermoelectric measurements unambiguously show that the FMOs in all the studied junctions are the highest occupied molecular orbitals and that the energetic separation decreases with increasing molecular length. Our computational studies of energetic separations and Seebeck coefficients of these AMMJs are in agreement with the experimentally obtained values and elucidate the electronic structure origins of the observed length dependence.

Influence of Non-stoichiometry on Proton Conductivity in Thin Film Yttrium-doped Barium Zirconate

Proton-conducting perovskites have been widely studied because of their potential application as solid electrolytes in intermediate temperature solid oxide fuel cells. Structural and chemical heterogeneities can develop during synthesis, device fabrication, or service, which can profoundly affect proton transport. Here, we use time-resolved Kelvin probe force microscopy, scanning transmission electron microscopy, atom probe tomography, and density functional theory calculations to intentionally introduce Ba-deficient planar and spherical defects and link the resultant atomic structure with proton transport behavior in both stoichiometric and nonstoichiometric epitaxial, yttrium-doped barium zirconate thin films. The defects were intentionally induced through high-temperature annealing treatment, while maintaining the epitaxial single crystalline structure of the films, with an overall relaxation in the atomic structure. The annealed samples showed smaller magnitudes of local lattice distortions because of the formation of proton polarons, thereby leading to decreased proton-trapping effect. This resulted in a decrease in the activation energy for proton transport, leading to faster proton transport.