Atomically precise graphene nanoribbons (GNRs) are a promising emerging class of designer quantum materials with electronic properties that are tunable by chemical design. However, many challenges remain in the device integration of these materials, especially regarding contacting strategies. We report on the device integration of uniaxially aligned and non-aligned 9-atom wide armchair graphene nanoribbons (9-AGNRs) in a field-effect transistor geometry using electron beam lithography-defined graphene electrodes. This approach yields controlled electrode geometries and enables higher fabrication throughput compared to previous approaches using an electrical breakdown technique. Thermal annealing is found to be a crucial step for successful device operation resulting in electronic transport characteristics showing a strong gate dependence. Raman spectroscopy confirms the integrity of the graphene electrodes after patterning and of the GNRs after device integration. Our results demonstrate the importance of the GNR-graphene electrode interface and pave the way for GNR device integration with structurally well-defined electrodes.

Unsupervised machine learning, and in particular data clustering, is a powerful approach for the analysis of datasets and identification of characteristic features occurring throughout a dataset. It is gaining popularity across scientific disciplines and is particularly useful for applications without a priori knowledge of the data structure. Here, we introduce an approach for unsupervised data classification of any dataset consisting of a series of univariate measurements. It is therefore ideally suited for a wide range of measurement types. We apply it to the field of nanoelectronics and spectroscopy to identify meaningful structures in data sets. We also provide guidelines for the estimation of the optimum number of clusters. In addition, we have performed an extensive benchmark of novel and existing machine learning approaches and observe significant performance differences. Careful selection of the feature space construction method and clustering algorithms for a specific measurement type can therefore greatly improve classification accuracies.

Graphene nanoribbons (GNRs) have attracted strong interest from researchers worldwide, as they constitute an emerging class of quantum-designed materials. The major challenges toward their exploitation in electronic applications include reliable contacting, complicated by their small size (<50 nm), and the preservation of their physical properties upon device integration. In this combined experimental and theoretical study, we report on the quantum dot behavior of atomically precise GNRs integrated in a device geometry. The devices consist of a film of aligned five-atom-wide GNRs (5-AGNRs) transferred onto graphene electrodes with a sub 5 nm nanogap. We demonstrate that these narrow-bandgap 5-AGNRs exhibit metal-like behavior at room temperature and single-electron transistor behavior for temperatures below 150 K. By performing spectroscopy of the molecular levels at 13 K, we obtain addition energies in the range of 200-300 meV. DFT calculations predict comparable addition energies and reveal the presence of two electronic states within the bandgap of infinite ribbons when the finite length of the 5-AGNR is accounted for. By demonstrating the preservation of the 5-AGNRs' molecular levels upon device integration, as demonstrated by transport spectroscopy, our study provides a critical step forward in the realization of more exotic GNR-based nanoelectronic devices.

In recent years, a wide range of single-molecule devices has been realized, enabled by technological advances combined with the versatility offered by synthetic chemistry. In particular, single-molecule diodes have attracted significant attention with an ongoing effort to increase the rectification ratio between the forward and reverse current. Various mechanisms have been investigated to improve rectification, either based on molecule-intrinsic properties or by engineering the coupling of the molecule to the electrodes. In this perspective, we first provide an overview of the current experimental approaches reported in literature to achieve rectification at the single-molecule level. We then proceed with our recent efforts in this direction, exploiting the internal structure of multi-site molecules, yielding the highest rectification ratio based on a molecule-intrinsic mechanism. We introduce the theoretical framework for multi-site molecules and infer general design guidelines from this. Based on these guidelines, a series of two-site molecules have been developed and integrated into devices. Using two- and three-terminal mechanically controllable break junction measurements, we show that depending on the on-site energies, which are tunable by chemical design, the devices either exhibit pronounced negative differential conductance, or behave as highly-efficient rectifiers. Finally, we propose a design of a single-molecule diode with a theoretical rectification ratio exceeding a million.

One of the main challenges to upscale the fabrication of molecular devices is to achieve a mechanically stable device with reproducible and controllable electronic features that operates at room temperature1,2. This is crucial because structural and electronic fluctuations can lead to significant changes in the transport characteristics at the electrode-molecule interface3,4. In this study, we report on the realization of a mechanically and electronically robust graphene-based molecular junction. Robustness was achieved by separating the requirements for mechanical and electronic stability at the molecular level. Mechanical stability was obtained by anchoring molecules directly to the substrate, rather than to graphene electrodes, using a silanization reaction. Electronic stability was achieved by adjusting the π-π orbitals overlap of the conjugated head groups between neighbouring molecules. The molecular devices exhibited stable current-voltage (I-V) characteristics up to bias voltages of 2.0 V with reproducible transport features in the temperature range from 20 to 300 K.

Single-molecule break-junction measurements are intrinsically stochastic in nature, requiring the acquisition of large datasets of “breaking traces” to gain insight into the generic electronic properties of the molecule under study. For example, the most probable conductance value of the molecule is often extracted from the conductance histogram built from these traces. In this letter, we present an unsupervised and reference-free machine learning tool to improve the determination of the conductance of oligo(phenylene ethynylene)dithiol from mechanically controlled break-junction (MCBJ) measurements. Our method allows for the classification of individual breaking traces based on an image recognition technique. Moreover, applying this technique to multiple merged datasets makes it possible to identify common breaking behaviors present across different samples, and therefore to recognize global trends. In particular, we find that the variation in the extracted molecular conductance can be significantly reduced resulting in a more reliable estimation of molecular conductance values from MCBJ datasets. Finally, our approach can be more widely applied to different measurement types which can be converted to two-dimensional images.

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.

A conformationally flexible calix[4]pyrrole possessing a conjugated electronic structure (an N-substituted oxoporphyrinogen (OxP) related to porphyrin) was used to investigate the influence of mechanical stretching on the single-molecule conductance of these molecules using the mechanically-controlled break junction (MCBJ) technique. The results show that the molecule can be immobilized in a single-molecule break junction configuration, giving rise to different behaviours. These include step-like features in the conductance vs. displacement traces as well as conductance traces that exhibit a slower decay (‘downhill’ traces) than measured for direct tunneling. The latter class of traces can be associated with the mechanical manipulation (i. e., stretching) of the molecule with inter-electrode distances as long as 2 nm. Density functional theory (DFT) calculations reveal that OxP molecules are stable under stretching in the length regime studied.

Expanded porphyrins are flexible enough to switch between different π-conjugation topologies, namely Möbius, Hückel and twisted-Hückel, each with distinct electronic properties and aromaticity. Since these switches can be induced by different external stimuli, expanded porphyrins represent a promising platform to develop a novel type of molecular switch for molecular electronic devices. In this work, the feasibility of conductance switches based on topology and/or aromaticity changes in expanded porphyrins is assessed for the first time. In particular, the electron transport properties of penta-, hexa- and heptaphyrins with different π-conjugation topologies and aromaticity were carefully investigated using the nonequilibrium Green's function formalism in combination with density functional theory for various configurations of the gold contacts. Our results highlight the importance of the macrocyclic aromaticity and connectivity and, to a lesser extent, the molecular topology, in determining the transmission functions and local currents. When the electrodes are connected along the longitudinal axis of the macrocycle, we found that aromaticity of Hückel expanded porphyrins increases single-molecule junction conductance, contrary to the negative relationship between conductance and aromaticity found in single five-membered rings. For this particular connectivity, antiaromatic Hückel structures with [4n] π-electrons exhibit a sharp reduction in transmission near the Fermi level due to destructive quantum interference between the HOMO and LUMO. Belt-shaped Möbius aromatic structures exhibit a lower conductance as compared to the Hückel aromatic structures, and the current flow avoids the molecular twist. Importantly, we show that expanded porphyrins, upon redox and topology interconversions, could act as efficient three-level molecular switches with high ON/OFF ratio, up to 10³ at low bias voltage.

We propose the design of a single-molecule diode with a rectification ratio exceeding a million. The employed mechanism is based on coherent resonant charge transport across a molecule that consists of four conjugated sites coupled by non-conjugated bridges. Using density functional theory calculations, we rationalize the design of the molecule and demonstrate the crucial role of aligning the sites at a specific voltage. Rectification ratios are calculated for a series of chemical substituents and demonstrate that with careful molecular design, high rectification ratios can be achieved. Finally, we comment on the shortcomings of our approach, how further improvements can be obtained and discuss some of the experimental challenges.

We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2. Theoretical calculations show the same trend. Self-assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single-molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.

We report on an approach to realize carbon-gold (C-Au) bonded molecular junctions without the need for an additive to deprotect the alkynyl carbon as endstanding anchor group. Using the mechanically controlled break junction (MCBJ) technique, we determine the most probable conductance value of a family of alkynyl terminated oligophenylenes (OPA(n)) connected to gold electrodes through such an akynyl moiety in ambient conditions. The molecules bind to the gold leads through an sp-hybridized carbon atom at each side. Comparing our results with other families of molecules that present organometallic C-Au bonds, we conclude that the conductance of molecules contacted via an sp-hybridized carbon atom is lower than the ones using sp³ hybridization due to strong differences in the coupling of the conducting orbitals with the gold leads.

Rectification has been at the foundation of molecular electronics. Most single-molecule diodes realized experimentally so far are based on asymmetries in the coupling with the electrodes or using the donor-acceptor principle. In general, however, their rectification ratios are usually small (<10). Here, we propose a single-molecule diode based on an orbital resonance while using the highest occupied molecular orbital (HOMO) and HOMO-1 as transport channels. Our proposed diode design is based on an asymmetric two-site model and analyzed with DFT + NEGF calculations. We find high rectification ratios, even in the case of symmetric coupling to the electrodes. In addition, we show that diode parameters such as the operating voltage and rectification ratio can be tuned by chemical design.