Orientational Effects and Molecular-Scale Thermoelectricity Control.

The orientational effect concept in a molecular-scale junction is established for asymmetric junctions, which requires the fulfillment of two conditions: (1) design of an asymmetric molecule with strong distinct terminal end groups and (2) construction of a doubly asymmetric junction by placing an asymmetric molecule in an asymmetric junction to form a multicomponent system such as Au/Zn-TPP+M/Au. Here, we demonstrate that molecular-scale junctions that satisfy the conditions of these effects can manifest Seebeck coefficients whose sign fluctuates depending on the orientation of the molecule within the asymmetric junction in a complete theoretical investigation. Three anthracene-based compounds are investigated in three different scenarios, one of which displays a bithermoelectric behavior due to the presence of strong anchor groups, including pyridyl and thioacetate. This bithermoelectricity demonstration implies that if molecules with alternating orientations can be placed between an asymmetric source and drain, they can be potentially utilized for increasing the thermovoltage in molecular-scale thermoelectric energy generators (TEGs).

Quantum Interference and Contact Effects in the Thermoelectric Performance of Anthracene-Based Molecules.

We report on the single-molecule electronic and thermoelectric properties of strategically chosen anthracene-based molecules with anchor groups capable of binding to noble metal substrates, such as gold and platinum. Specifically, we study the effect of different anchor groups, as well as quantum interference, on the electric conductance and the thermopower of gold/single-molecule/gold junctions and generally find good agreement between theory and experiments. All molecular junctions display transport characteristics consistent with coherent transport and a Fermi alignment approximately in the middle of the highest occupied molecular orbital/lowest unoccupied molecular orbital gap. Single-molecule results are in agreement with previously reported thin-film data, further supporting the notion that molecular design considerations may be translated from the single- to many-molecule devices. For combinations of anchor groups where one binds significantly more strongly to the electrodes than the other, the stronger anchor group appears to dominate the thermoelectric behavior of the molecular junction. For other combinations, the choice of electrode material can determine the sign and magnitude of the thermopower. This finding has important implications for the design of thermoelectric generator devices, where both n- and p-type conductors are required for thermoelectric current generation.