Full thermoelectric characterization of a single molecule.

Molecules are predicted to be chemically tunable towards high thermoelectric efficiencies and they could outperform existing materials in the field of energy conversion. However, their capabilities at the more technologically relevant temperature of 300 K are yet to be demonstrated. A possible reason could be the lack of a comprehensive technique able to measure the thermal and (thermo)electrical properties, including the role of phonon conduction. Here, by combining the break junction technique with a suspended heat-flux sensor, we measured the total thermal and electrical conductance of a single molecule, at room temperature, together with its Seebeck coefficient. We used this method to extract the figure of merit zT of a tailor-made oligo(phenyleneethynylene)-9,10-anthracenyl molecule with dihydrobenzo[b]thiophene anchoring groups (DHBT-OPE3-An), bridged between gold electrodes. The result is in excellent agreement with predictions from density functional theory and molecular dynamics. This work represents the first measurement, within the same setup, of experimental zT of a single molecule at room temperature and opens new opportunities for the screening of several possible molecules in the light of future thermoelectric applications. The protocol is verified using SAc-OPE3, for which individual measurements for its transport properties exist in the literature.

Thermal Transport through Single-Molecule Junctions.

Molecular junctions exhibit a rich and tunable set of thermal transport phenomena. However, the predicted high thermoelectric efficiencies, phonon quantum interference effects, rectification, and nonlinear heat transport properties of organic molecules are yet to be verified because suitable experimental techniques have been missing. Here, by combining the break junction technique with suspended heat-flux sensors with picowatt per Kelvin sensitivity, we measured the thermal and electrical conductance of single organic molecules at room temperature simultaneously. We used this method to study the thermal transport properties of two model systems, namely, dithiol-oligo(phenylene ethynylene) and octane dithiol junctions with gold electrodes. In agreement with our density functional theory and phase-coherent transport calculations, we show that heat transport across these systems is governed by the phonon mismatch between the molecules and the metallic electrodes. This work represents the first measurement of thermal transport through single molecules and opens new opportunities for studying heat management at the nanoscale level.

Crystallization of a Two-Dimensional Hydrogen-Bonded Molecular Assembly: Evolution of the Local Structure Resolved by Atomic Force Microscopy.

Structures of the aromatic N-heterocyclic hexaazatriphenylene (HAT) molecular synthon obtained by surface-assisted self-assembly were analyzed with sub-Å resolution by means of noncontact atomic force microscopy (nc-AFM), both in the kinetically trapped amorphous state and in the thermodynamically stable crystalline phase. These results reveal how the crystallization governs the length scale of the network order for non-flexible molecular species without affecting the local bonding schemes. The capability of nc-AFM to accurately resolve structural relaxations will be highly relevant for the characterization of vitreous two-dimensional supramolecular materials.

Heat transport through atomic contacts.

Heat transport and dissipation at the nanoscale severely limit the scaling of high-performance electronic devices and circuits. Metallic atomic junctions serve as model systems to probe electrical and thermal transport down to the atomic level as well as quantum effects that occur in one-dimensional (1D) systems. Whereas charge transport in atomic junctions has been studied intensively in the past two decades, heat transport remains poorly characterized because it requires the combination of a high sensitivity to small heat fluxes and the formation of stable atomic contacts. Here we report heat-transfer measurements through atomic junctions and analyse the thermal conductance of single-atom gold contacts at room temperature. Simultaneous measurements of charge and heat transport reveal the proportionality of electrical and thermal conductance, quantized with the respective conductance quanta. This constitutes a verification of the Wiedemann-Franz law at the atomic scale.