Helical molecules have been proposed as candidates for producing spin-polarized currents, even at room conditions, due to their chiral asymmetry. However, describing their transport mechanism in single molecular junctions is not straightforward. In this work, we show the synthesis of two novel kinds of dithia[11]helicenes to study their electronic transport in break junctions among a series of three helical molecules: dithia[n]helicenes, with n = 7, 9, and 11 molecular units. Our experimental measurements and clustering-based analysis demonstrate low conductance values that remain similar across different applied voltages and molecules. Additionally, we assess the length dependence of the conductance for each helicene, revealing an exponential decay characteristic of off-resonant transport. This behavior is primarily attributed to the misalignment between the energy levels of the molecule-electrodes system. The length dependence trend described above is supported by ab initio calculations, further confirming an off-resonant transport mechanism.

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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.@en

Creating a good contact between electrodes and graphene nanoribbons (GNRs) has been a long-standing challenge in searching for the next GNR-based nanoelectronics. This quest requires the controlled fabrication of sub-20 nm metallic gaps, a clean GNR transfer minimizing damage and organic contamination during the device fabrication, as well as work function matching to minimize the contact resistance. Here, we transfer 9-atom-wide armchair-edged GNRs (9-AGNRs) grown on Au(111)/mica substrates to pre-patterned platinum electrodes, yielding polymer-free 9-AGNR field-effect transistor devices. Our devices have a resistance in the range of 10⁶-10⁸ Ω in the low-bias regime, which is 2-4 orders of magnitude lower than previous reports. Density functional theory calculations combined with the non-equilibrium Green's function method explain the observed p-type electrical characteristics and further demonstrate that platinum gives strong coupling and higher transmission in comparison to other materials, such as graphene.

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Thermocurrent flowing through a single-molecule device contains valuable information about the quantum properties of the molecular structure and, in particular, on its electronic and phononic excitation spectra and entropy. Furthermore, accessing the thermoelectric heat-to-charge conversion efficiency experimentally can help to select suitable molecules for future energy conversion devices, which - predicted by theoretical studies - could reach unprecedented efficiencies. However, one of the major challenges in quantifying thermocurrents in nanoscale devices is to determine the exact temperature bias applied to the junction. In this work, we have incorporated a superconductor-normal metal-superconductor Josephson junction thermometer into a single-molecule device. The critical current of the Josephson junction depends accurately on minute changes in the electronic temperature in a wide temperature range from 100 mK to 1.6 K. Thus, we present a device architecture which can enable thermoelectric experiments on single molecules down to millikelvin temperatures with high precision.

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Probing the universal low-temperature magnetic-field scaling of Kondo-correlated quantum dots via electrical conductance has proved to be experimentally challenging. Here, we show how to probe this in nonlinear thermocurrent spectroscopy applied to a molecular quantum dot in the Kondo regime. Our results demonstrate that the bias-dependent thermocurrent is a sensitive probe of universal Kondo physics, directly measures the splitting of the Kondo resonance in a magnetic field, and opens up possibilities for investigating nanosystems far from thermal and electrical equilibrium.

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The possibility to study quantum interference phenomena at ambient conditions is an appealing feature of molecular electronics. By connecting two porphyrins in a cofacial cyclophane, we create an attractive platform for mechanically controlling electric transport through the intramolecular extent of π-orbital overlap of the porphyrins facing each other and through the angle of xanthene bridges with regard to the porphyrin planes. We analyze theoretically the evolution of molecular configurations in the pulling process and the corresponding changes in electric conduction by combining density functional theory (DFT) with Landauer scattering theory of phase-coherent elastic transport. Predicted conductances during the stretching process show order of magnitude variations caused by two robust destructive quantum interference features that span through the whole electronic gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Mechanically-controlled break junction (MCBJ) experiments at room temperature verify the mechanosensitive response of the molecular junctions. During the continuous stretching of the molecule, they show conductance variations of up to 1.5 orders of magnitude over single breaking events. Uncommon triple-and quadruple-frequency responses are observed in periodic electrode modulation experiments with amplitudes of up to 10 Å. This further confirms the theoretically predicted double transmission dips caused by the spatial and energetic rearrangement of molecular orbitals, with contributions from both through-space and through-bond transport. This journal is

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As the miniaturization of electronics continuously progresses, harvesting and generating thermoelectric energy with high efficiency become a key concept to integrate. Theoretical studies suggest that single-molecule devices are ideal candidates for thermoelectric devices with unprecedentedly high efficiencies. Such advantage is achieved by molecular designs with ideal energy alignment, optimized tunnel coupling or strong quantum interference features, etc. In our single-molecule thermoelectric devices, we have demonstrated the possibility to extract important thermoelectric functions such as Seebeck coefficient and the power factor. In addition, we can obtain crucial physical parameters in single-molecule devices such as the entropy changes, excited states or the universality of the Kondo effect via the thermoelectric study. We expect, as our works have shown, thermoelectric studies in single-molecule devices will bring us more useful innovative devices and more fundamental understanding of nanoscale systems.@en

This dissertation presents the experimental work on singlemolecule charge transport, particularly on the aspects of spin and orbital conformational effects in singlemolecule junctions. In this dissertation, we employ and develop various singlemolecule techniques, the mechanically controlled break junction (MCBJ), thermoelectric electromigrated break junction (ThEMBJ) and reversible spin Hall junction (RSHJ), to characterize the spin and conformational effects beyond simple charge transport.@en

Intra- and intermolecular interactions are dominating chemical processes, and their concerted interplay enables complex nonequilibrium states like life. While the responsible basic forces are typically investigated spectroscopically, a conductance measurement to probe and control these interactions in a single molecule far out of equilibrium is reported here. Specifically, by separating macroscopic metal electrodes, two π-conjugated, bridge-connected porphyrin decks are peeled off on one side, but compressed on the other side due to the covalent mechanical fixation. We observe that the conductance response shows an exceptional exponential rise by two orders of magnitude in individual breaking events during the stretching. Theoretical studies atomistically explain the measured conductance behavior by a mechanically activated increase in through-bond transport and a simultaneous strengthening of through-space coupling. Our results not only reveal the various interacting intramolecular transport channels in a molecular set of levers, but also the molecules' potential to serve as molecular electro-mechanical sensors and switches.@en

Quantum interference (QI) of electron waves passing through a single-molecule junction provides a powerful means to influence its electrical properties. Here, we investigate the correlation between substitution pattern, conductance, and mechanosensitivity in [2.2]paracyclophane (PCP)-based molecular wires in a mechanically controlled break junction experiment. The effect of the meta versus para connectivity in both the central PCP core and the phenyl ring connecting the terminal anchoring group is studied. We find that the meta-phenyl-anchored PCP yields such low conductance levels that molecular features cannot be resolved; in the case of para-phenyl-coupled anchoring, however, large variations in conductance values for modulations of the electrode separation occur for the pseudo-para-coupled PCP core, while this mechanosensitivity is absent for the pseudo-meta-PCP core. The experimental findings are interpreted in terms of QI effects between molecular frontier orbitals by theoretical calculations based on density functional theory and the Landauer formalism.

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Quantum interference (QI) within a single-molecule junction has become an essential yet powerful concept to integrate for designing molecular electronic devices.1 Recently we have investigated the correlation between substitution pattern, conductance and mechanosensitivity in [2.2]paracyclophane(PCP)-based single-molecule junction via the mechanically controlled break junction technique (MCBJ).2,3 We study the influence on conductance when we introduce meta/para connection to the PCP core and the phenyl ring attached to the anchoring group. We find that (i) meta-phenyl-anchored PCP yields such low conductance levels that molecular features cannot be resolved; (ii) para-phenyl-coupled anchoring generally gives higher conductance levels which can be detected via MCBJ; (iii) pseudo-para-coupled PCP core manifests large mechanosensitivity while (iv) pseudo-meta-coupled PCP core show the absence of mechanosensitivity. These experimental findings are interpreted in terms of QI effects between molecular frontier orbitals by theoretical calculations based on density functional theory and the Landauer formalism.@en

Theoretical studies suggest that mastering the thermocurrent through single molecules can lead to thermoelectric energy harvesters with unprecedentedly high efficiencies.^1–6 This can be achieved by engineering molecule length,⁷ optimizing the tunnel coupling strength of molecules via chemical anchor groups⁸ or by creating localized states in the backbone with resulting quantum interference features.⁴ Empirical verification of these predictions, however, faces considerable experimental challenges and is still awaited. Here we use a novel measurement protocol that simultaneously probes the conductance and thermocurrent flow as a function of bias voltage and gate voltage. We find that the resulting thermocurrent is strongly asymmetric with respect to the gate voltage, with evidence of molecular excited states in the thermocurrent Coulomb diamond maps. These features can be reproduced by a rate-equation model only if it accounts for both the vibrational coupling and the electronic degeneracies, thus giving direct insight into the interplay of electronic and vibrational degrees of freedom, and the role of spin entropy in single molecules. Overall these results show that thermocurrent measurements can be used as a spectroscopic tool to access molecule-specific quantum transport phenomena.

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Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, not detected by conventional charge transport measurements. This highlights the power of thermoelectric measurements which can be used to determine the difference in configurational entropy between the redox states of a nanoscale system involved in conductance without any prior assumptions about its structure or microscopic dynamics.

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Porphyrin cyclophane 1, consisting of two rigidly fixed but still movable cofacial porphyrins and exposing acetate-masked thiols in opposed directions of the macrocycle, is designed, synthesized, and characterized. The functional cyclophane 1, as pioneer of mechanosensitive 3D materials, forms stable single-molecule junctions in a mechanically controlled break-junction setup. Its reliable integration in a single-molecule junction is a fundamental prerequisite to explore the potential of these structures as mechanically triggered functional units and devices.

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We fabricated large-area atomically thin MoS₂ layers through the direct transformation of crystalline molybdenum trioxide (MoO₃) by sulfurization at relatively low temperatures. The obtained MoS₂ sheets are polycrystalline (~10-20 nm single-crystal domain size) with areas of up to 300 × 300 μm2, 2-4 layers in thickness and show a marked p-type behavior. The synthesized films are characterized by a combination of complementary techniques: Raman spectroscopy, X-ray diffraction, transmission electron microscopy and electronic transport measurements.

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An interesting aspect of 2D materials is the change of their electronic structure with the reduction of thickness. Molybdenum and tungsten-based transition metal dichalcogenides form an important family of 2D materials, whose members show a thickness-dependent bandgap and strong light–matter interaction. In this work, the experimental determination of the complex refractive index of 1-, 2-, 3-layer thick MoS ₂ , MoSe ₂ , WS ₂ , and WSe ₂ in the range from 400 to 850 nm of the electromagnetic spectrum is reported by using microreflectance spectroscopy and combined with calculations based on the Fresnel equations. It is further provided a comparison with the bulk refractive index values reported in the literature and a discussion of the difference/similarity between our work and the monolayer refractive index available from the literature, finding that the results from different techniques are in good agreement.

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A great interest of molecular electronics comes from its change in electronic structure through external stimuli, which provides functionality at the single-molecule level. Mechanically-controlled break junction (MCBJ) is a great tool for characterizing molecular properties and their response to different stimuli including light, solvent and importantly, mechanical deformation1. In our recent MCBJ experiment, we showed that the conductance of a spring-like molecule can be mechanically tuned up to an order of magnitude at room temperature2. The physical origin of such feature is a consequence of destructive quantum interference between the frontier orbitals. This indicates not only a possible application for mechanical sensors based on this class of molecules, but also demonstrates a good example of quantum interference effect in single molecules. Following this intriguing result, we investigate other properties of this molecule, such as I-V characteristics at low temperature and thermopower. We are also exploring other molecules with similar spring-like structures, where quantum interference effect is expected to manifest. @en

An appealing feature of molecular electronics is the possibility of inducing changes in the orbital structure through external stimuli. This can provide functionality on the single-molecule level that can be employed for sensing or switching purposes if the associated conductance changes are sizable upon application of the stimuli. Here, we show that the room-temperature conductance of a spring-like molecule can be mechanically controlled up to an order of magnitude by compressing or elongating it. Quantum-chemistry calculations indicate that the large conductance variations are the result of destructive quantum interference effects between the frontier orbitals that can be lifted by applying either compressive or tensile strain to the molecule. When periodically modulating the electrode separation, a conductance modulation at double the driving frequency is observed, providing a direct proof for the presence of quantum interference. Furthermore, oscillations in the conductance occur when the stress built up in the molecule is high enough to allow the anchoring groups to move along the surface in a stick-slip-like fashion. The mechanical control of quantum interference effects results in the largest-gauge factor reported for single-molecule devices up to now, which may open the door for applications in, e.g., a nanoscale mechanosensitive sensing device that is functional at room temperature.

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