Benchmarking break-junction techniques: electric and thermoelectric characterization of naphthalenophanes.

Break-junction techniques provide the possibility to study electric and thermoelectric properties of single-molecule junctions in great detail. These techniques rely on the same principle of controllably breaking metallic contacts in order to create single-molecule junctions, whilst keeping track of the junction's conductance. Here, we compare results from mechanically controllable break junction (MCBJ) and scanning tunneling microscope (STM) methods, while characterizing conductance properties of the same novel mechanosensitive para- and meta-connected naphtalenophane compounds. In addition, thermopower measurements are carried out for both compounds using the STM break junction (STM-BJ) technique. For the conductance experiments, the same data processing using a clustering analysis is performed. We obtain to a large extent similar results for both methods, although values of conductance and stretching lengths for the STM-BJ technique are slightly larger in comparison with the MCBJ. STM-BJ thermopower experiments show similar Seebeck coefficients for both compounds. An increase in the Seebeck coefficient is revealed, whilst the conductance decreases, after which it saturates at around 10 µV K-1. This phenomenon is studied theoretically using a tight binding model. It shows that changes of molecule-electrode electronic couplings combined with shifts of the resonance energies explain the correlated behavior of conductance and Seebeck coefficient.

Influence of Peripheral Alkyl Groups on Junction Configurations in Single-Molecule Electronics.

The addition of a lateral alkyl chain is a well-known strategy to reduce π-stacked ensembles of molecules in solution, with the intention to minimize the interactions between the molecules' backbones. In this paper, we study whether this concept generalizes to single-molecule junctions by using a combination of mechanically controllable break junction (MCBJ) measurements and clustering-based data analysis with two small series of model compounds decorated with various bulky groups. The systematic study suggests that introducing alkyl side chains also favors the formation of electrode-molecule configurations that are not observed in their absence, thereby inducing broadening of the conductance peak in the one-dimensional histograms. Thus, the introduction of alkyl chains in aromatic compounds for molecular electronics must be carefully designed and optimized for the specific purpose, balancing between increased solubility and the possibility of additional junction configurations.

Spin-Crossover in Supramolecular Iron(II)-2,6-bis(1H-Pyrazol-1-yl)pyridine Complexes: Toward Spin-State Switchable Single-Molecule Junctions.

Spin-crossover (SCO) active iron(II) complexes are an integral class of switchable and bistable molecular materials. Spin-state switching properties of the SCO complexes have been studied in the bulk and single-molecule levels to progress toward fabricating molecule-based switching and memory elements. Supramolecular SCO complexes featuring anchoring groups for metallic electrodes, for example, gold (Au), are ideal candidates to study spin-state switching at the single-molecule level. In this study, we report on the spin-state switching characteristics of supramolecular iron(II) complexes 1 and 2 composed of functional 4-([2,2'-bithiophen]-5-ylethynyl)-2,6-di(1H-pyrazol-1-yl)pyridine (L1) and 4-(2-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)ethynyl)-2,6-di(1H-pyrazol-1-yl)pyridine (L2) ligands, respectively. Density functional theory (DFT) studies revealed stretching-induced spin-state switching in a molecular junction composed of complex 1, taken as a representative example, and gold electrodes. Single-molecule conductance traces revealed the unfavorable orientation of the complexes in the junctions to demonstrate the spin-state dependence of the conductance.

3.9 THz spatial filter based on a back-to-back Si-lens system.

We present a terahertz spatial filter consisting of two back-to-back (B2B) mounted elliptical silicon lenses and an opening aperture defined on a thin gold layer between the lenses. The beam filtering efficiency of the B2B lens system is investigated by simulation and experiment. Using a unidirectional antenna coupled 3rd-order distributed feedback (DFB) quantum cascade laser (QCL) at 3.86 THz as the source, the B2B lens system shows 72% transmissivity experimentally with a fundamental Gaussian mode as the input, in reasonably good agreement with the simulated value of 80%. With a proper aperture size, the B2B lens system is capable of filtering the non-Gaussian beam from the QCL to a nearly fundamental Gaussian beam, where Gaussicity increases from 74% to 99%, and achieves a transmissivity larger than 30%. Thus, this approach is proven to be an effective beam shaping technique for QCLs, making them to be suitable local oscillators in the terahertz range with a Gaussian beam. Besides, the B2B lens system is applicable to a wide frequency range if the wavelength dependent part is properly scaled.