Molecular-scale Electronic Devices Research Articles

Remote-Controllable Interfacial Electron Tunneling at Heterogeneous Molecular Junctions via Tip-Induced Optoelectrical Engineering.

Molecular electronics enables functional electronic behavior via single molecules or molecular self-assembled monolayers, providing versatile opportunities for hybrid molecular-scale electronic devices. Although various molecular junction structures are constructed to investigate charge transfer dynamics, significant challenges remain in terms of interfacial charging effects and far-field background signals, which dominantly block the optoelectrical observation of interfacial charge transfer dynamics. Here, tip-induced optoelectrical engineering is presented that synergistically correlates photo-induced force microscopy and Kelvin probe force microscopyto remotely control and probe the interfacial charge transfer dynamics with sub-10nm spatial resolution. Based on this approach, the optoelectrical origin of metal-molecule interfaces is clearly revealed by the nanoscale heterogeneity of the tip-sample interaction and optoelectrical reactivity, which theoretically aligned with density functional theory calculations. For a practical device-scale demonstration of tip-induced optoelectrical engineering, interfacial tunneling is remotely controlled at a 4-inch wafer-scale metal-insulator-metal capacitor, facilitating a 5.211-fold current amplification with the tip-induced electrical field. In conclusion, tip-induced optoelectrical engineering provides a novel strategy to comprehensively understand interfacial charge transfer dynamics and a non-destructive tunneling control platform that enables real-time and real-space investigation of ultrathin hybrid molecular systems.

Nanoscale Surface Functionalization Based on Heterogeneous Self-Assembled Monolayers for Molecular-Scale Electronics.

Mixed self-assembled monolayers (mixed SAMs)-based molecular-scale electronic devices in recent years have gained great achievement in the fundamental study on charge transport mechanism and electronic functionalities. This review aims to summarize the preparation and characterization, structure modulation, and applications of heterogeneous mixed SAMs in molecular electronics. One key advantage of SAM-based molecular devices compared to single molecular devices is the ability to tune the intermolecular interactions, and two-dimensional (2-D) assembly structure allows for the optimization of charge transport in desired devices. Herein we review the qualitative and quantitative examination of the nanoscale organization and intermolecular interactions of mixed SAMs obtained by various mixed SAM preparation and characterization techniques. The use of mixed SAMs to control the structural order and compactness of SAM to form high-performance molecular electronic devices is also reviewed. Finally, we wrap up the review by discussing the challenges of this technique for the development of novel electronic functional devices in the future.

Electrically induced light emission via nanoscale vacuum discharge in nanogap electrodes without luminescent molecules

Understanding the mechanisms of electrically induced light emission in nanoscale junctions is crucial in molecular-scale optoelectronics. In this study, we investigated the light emission from nanogap electrodes with an insulating and nonluminescent material (polystyrene). Electrically induced light emission was observed over a wide wavelength range of 400–600 nm. The threshold voltages for the light emission ranged from 3 to 15 V, depending on the device, indicating that the electric field induced at the nanogap, rather than the applied potential, is the driving force for the light emission. The intensity of the light emission varies exponentially with the current with an exponent higher than 1.6, and the light emission is driven by a thermally activated current. These characteristics are inconsistent with the mechanisms reported for solid-state nanogap devices. We conclude that light emission in the nanogap electrodes is attributed to nanoscale vacuum discharge with metal plasma. The light emission from this mechanism can conflict with the other mechanisms ever reported since it occurs at such low voltages. The results also suggest intrinsic instability in molecular-scale electronic devices based on nanogap electrodes because the vacuum discharge is accompanied by the plasticization of the electrode.

Electronic Coupling in 1,2,3-Triazole Bridged Ferrocenes and Its Impact on Reactive Oxygen Species Generation and Deleterious Activity in Cancer Cells

Mixed-valence (MV) binuclear ferrocenyl compounds have long been studied as models for testing theories of electron transfer and in attempts to design molecular-scale electronic devices (e.g., molecular wires). In contrary to that, far less attention has been paid to MV binuclear ferrocenes as anticancer agents. Herein, we discuss the synthesis of six 1,2,3-triazole ferrocenyl compounds for combined (spectro)electrochemical, electron paramagnetic resonance (EPR), computational, and anticancer activity studies. Our synthetic approach was based on the copper-catalyzed 1,3-dipolar azide–alkyne cycloaddition reaction and enabled us to obtain in one step compounds bearing either one, two, or three ferrocenyl entities linked to the common 1,2,3-triazole core. Thus, two series of complexes were obtained, which pertain to derivatives of 3′-azido-3′-deoxythymidine (AZT) and 3-azidopropionylferrocene, respectively. Based on the experimental and theoretical data, the two mono-oxidized species corresponding to binuclear AZT and trinuclear 3-azidopropionylferrocene complexes have been categorized as class II mixed-valence according to the classification proposed by Robin and Day. Of importance is the observation that these two compounds are more active against human A549 and H1975 non-small-cell lung cancer cells than their congeners, which do not show MV characteristics. Moreover, the anticancer activity of MV species competes or surpasses, dependent on the cell line, the activity of reference anticancer drugs such as cisplatin, tamoxifen, and 5-fluorouracil. The most active from the entire series of compounds was the binuclear thymidine derivative with the lowest IC50 value of 5 ± 2 μM against lung H1975 cancer cells. The major mechanism of antiproliferative activity for the investigated MV compounds is based on reactive oxygen species generation in cancer cells. This hypothesis was substantiated by EPR spin-trapping experiments and the observation of decreased anticancer activity in the presence of N-acetyl cysteine (NAC) free-radical scavenger.

Light-Driven Charge Transport and Optical Sensing in Molecular Junctions.

Probing charge and energy transport in molecular junctions (MJs) has not only enabled a fundamental understanding of quantum transport at the atomic and molecular scale, but it also holds significant promise for the development of molecular-scale electronic devices. Recent years have witnessed a rapidly growing interest in understanding light-matter interactions in illuminated MJs. These studies have profoundly deepened our knowledge of the structure–property relations of various molecular materials and paved critical pathways towards utilizing single molecules in future optoelectronics applications. In this article, we survey recent progress in investigating light-driven charge transport in MJs, including junctions composed of a single molecule and self-assembled monolayers (SAMs) of molecules, and new opportunities in optical sensing at the single-molecule level. We focus our attention on describing the experimental design, key phenomena, and the underlying mechanisms. Specifically, topics presented include light-assisted charge transport, photoswitch, and photoemission in MJs. Emerging Raman sensing in MJs is also discussed. Finally, outstanding challenges are explored, and future perspectives in the field are provided.

Multiple heteroatom substitution effect on destructive quantum interference in tripodal single-molecule junctions.

Quantum interference (QI) has been identified as a promising strategy for designing molecular-scale electronic devices. Heteroatom doping can effectively tailor the local structures and electronic states of intrinsic molecules, and endow them with modified electron transport properties. Herein, the impacts of multiple heteroatom substitution on destructive quantum interference (DQI) have been investigated based on tripodal meta-linked phenyl derivatives. Orbital views based on the Hückel method qualitatively predict the meta-anchored molecules with DQI features, while the introduction of nitrogen atoms can alleviate the suppression of DQI at the Fermi level (EF). This is generally consistent with the movement or even removal of the antiresonance dips in transmission spectra. The substituent on position 2 can raise the antiresonance energy, while the substituent on position 4 or 6 can lower the antiresonance energy. When more than one nitrogen atom is incorporated, the impact of the substitution on positions 4 and 6 can be superimposed and the substitution on positions 2 and 4 can be partly cancelled. The experimental single-molecule conductance for tripodal molecules follows the trend of 0N-3SMe < 1N-3SMe < 3N-3SMe < 2N-3SMe, in agreement with the theoretical prediction. Additionally, the regulation is the intrinsic property depending on the position and number of the nitrogen atoms in the backbone and is irrelevant to the number and type of the anchoring groups. Our findings provide qualitative guidance for tuning the electron transport based on DQI in heterocycle molecular devices.

Determination of the preferred reaction pathway of acetophenone on Si(001) using photoelectron diffraction

The adsorption configurations of a technologically relevant model organic adsorbate on the silicon (001) surface were studied using energy scanned x-ray photoelectron diffraction (PhD). Previous work has established the existence of an interesting vertically-aligned (‘flagpole’) configuration, where the acetophenone attaches to Si(001) via the acetyl group carbon and oxygen atoms. Density functional theory calculations have predicted two energetically similar variants of this structure, where the phenyl ring is orientated parallel or perpendicular to the rows of silicon dimers on this reconstructed surface. However, previously published experimental measurements, including scanning tunnelling microscopy, x-ray photoelectron spectroscopy, and near-edge x-ray absorption fine structure investigations were unable to distinguish between these two configurations. Here, we apply the unique experimental capabilities of the PhD technique to this system and demonstrate that the dominant adsorption configuration has the phenyl ring parallel to the dimer rows (the end-bridge structure). This information in turn facilitates the determination of the dominant reaction pathway for acetophenone on Si(001), which has remained elusive until now. Information about subtle preferences in reaction pathways that affect the alignment and orientation of organic adsorbates such as acetophenone on technologically-relevant semiconductor surfaces such as Si(001) is critical for the fabrication of future atomically-precise atomic and molecular-scale electronic devices utilising the organic-silicon interface, and this work demonstrates the unique and complementary capabilities of PhD for providing this information.

Interstitially Mixed Self-Assembled Monolayers Enhance Electrical Stability of Molecular Junctions.

Electrical breakdown is a critical problem in electronics. In molecular electronics, it becomes more problematic because ultrathin molecular monolayers have delicate and defective structures and exhibit intrinsically low breakdown voltages, which limit device performances. Here, we show that interstitially mixed self-assembled monolayers (imSAMs) remarkably enhance electrical stability of molecular-scale electronic devices without deteriorating function and reliability. The SAM of the sterically bulky matrix (SC11BIPY rectifier) molecule is diluted with a skinny reinforcement (SCn) molecule via the new approach, so-called repeated surface exchange of molecules (ReSEM). Combined experiments and simulations reveal that the ReSEM yields imSAMs wherein interstices between the matrix molecules are filled with the reinforcement molecules and leads to significantly enhanced breakdown voltage inaccessible by traditional pure or mixed SAMs. Thanks to this, bias-driven disappearance and inversion of rectification is unprecedentedly observed. Our work may help to overcome the shortcoming of SAM's instability and expand the functionalities.

Charge transport through extended molecular wires with strongly correlated electrons.

Electron–electron interactions are at the heart of chemistry and understanding how to control them is crucial for the development of molecular-scale electronic devices. Here, we investigate single-electron tunneling through a redox-active edge-fused porphyrin trimer and demonstrate that its transport behavior is well described by the Hubbard dimer model, providing insights into the role of electron–electron interactions in charge transport. In particular, we empirically determine the molecule's on-site and inter-site electron–electron repulsion energies, which are in good agreement with density functional calculations, and establish the molecular electronic structure within various oxidation states. The gate-dependent rectification behavior confirms the selection rules and state degeneracies deduced from the Hubbard model. We demonstrate that current flow through the molecule is governed by a non-trivial set of vibrationally coupled electronic transitions between various many-body ground and excited states, and experimentally confirm the importance of electron–electron interactions in single-molecule devices.

Redox Control of Charge Transport in Vertical Ferrocene Molecular Tunnel Junctions

Summary Controlling charge transport through molecular tunnel junctions is of crucial importance for exploring basic physical and chemical mechanisms at the molecular level and realizing the applications of molecular devices. Here, through a combined experimental and theoretical investigation, we demonstrate redox control of cross-plane charge transport in a vertical gold/self-assembled monolayer (SAM)/graphene tunnel junction composed of a ferrocene-based SAM. When an oxidant/reductant or electrochemical control is applied to the outside surface of the neutral single-layer graphene top electrode, reversible redox reactions of ferrocene groups take place with charges crossing the graphene layer. This leads to counter anions on the outer surface of graphene, which balance the charges of ferrocene cations in the oxidized state. Correspondingly, the junctions switch between a high-conductance, neutral state with asymmetrical characteristics and a low-conductance, oxidized state with symmetrical characteristics, yielding a large on/off ratio (>100).

Molecular Rectifiers on Silicon: High Performance by Enhancing Top-Electrode/Molecule Coupling.

One of the simplest molecular-scale electronic devices is the molecular rectifier. In spite of considerable efforts aimed at understanding structure-property relationships in these systems, devices with predictable and stable electronic properties are yet to be developed. Here, we demonstrate highly efficient current rectification in a new class of compounds that form self-assembled monolayers on silicon. We achieve this by exploiting the coupling of the molecules with the top electrode which, in turn, controls the position of the relevant molecular orbitals. The molecules consist of a silane anchoring group and a nitrogen-substituted benzene ring, separated by a propyl group and imine linkage, and result from a simple, robust, and high-yield synthetic procedure. We find that when incorporated in molecular diodes, these compounds can rectify current by as much as 3 orders of magnitude, depending on their structure, with a maximum rectification ratio of 2635 being obtained in ( E)-1-(4-cyanophenyl)- N-(3-(triethoxysilyl) propyl)methanimine (average Ravg = 1683 ± 458, at an applied voltage of 2 V). This performance is on par with that of the best molecular rectifiers obtained on metallic electrodes, but it has the advantage of lower cost and more efficient integration with current silicon technologies. The development of molecular rectifiers on silicon may yield hybrid systems that can expand the use of silicon toward novel functionalities governed by the molecular species grafted onto its surface.

Thermally Controlled Phase Transition of Low-Melting Electrode for Wetting-Based Spontaneous Top Contact in Molecular Tunnel Junction.

Top contacts for molecular-scale electronic devices should exhibit reliable and reproducible electronic performance. This goal is challenging and difficult to achieve because metals are usually evaporated under high-energy conditions that easily damage delicate organic surfaces, and complicated nanofabrication processes are needed for achieving geometrically defined small contact areas. Soft top contacts that are made by users under ambient conditions can circumvent this problem but often show user-dependence. This paper describes that thermally controlled phase transition (TCPT) of low-melting (29.76 °C) electrode comprising gallium covered with a self-passivating oxide layer could be useful to form reliable, spontaneous (i.e., user-independent) top contacts over delicate ultrathin organic films such as self-assembled monolayers (SAMs). As a proof-of-concept, we demonstrate that the phase transition from solid to non-Newtonian liquid for gallium electrode is tuned under mild thermal conditions (room temperature to ∼50 °C), which does not damage the organic component and ensures conformal, geometrically defined contacts. The contact force predominantly depends on wetting of compliant liquid gallium onto SAMs, upon heating, not on user-pressure. Indeed, the TCPT-based large-area tunnel junctions on SAMs of n-mercaptoalkanoic acids yield markedly narrow dispersion of tunneling current density (σlog| J| = 0.04-0.19) and tunneling attenuation coefficient (β = 0.92 ± 0.02 nC-1) consistent with the literature value. We envisage that our approach can be harnessed to accomplish liquid metal-based tunnel junctions without significant user-to-user variations and hence useful for reliable understanding of charge transport across molecules and practical applications.

Elucidating the Role of Molecule-Electrode Interfacial Defects in Charge Tunneling Characteristics of Large-Area Junctions.

Interfacial chemistry at organic-inorganic contact critically determines the function of a wide range of molecular and organic electronic devices and other systems. The chemistry is, however, difficult to understand due to the lack of easily accessible in-operando spectroscopic techniques that permit access to interfacial structure on a molecular scale. Herein, we compare two analogous junctions formed with identical organic thin film and different liquid top-contacts (water droplet vs eutectic gallium indium alloy) and elucidate the puzzling interfacial characteristics. Specifically, we fine-tune the surface topography of the organic surface using mixed self-assembled monolayers (SAMs): single component SAM composed of rectifier (2,2'-bipyridyl-terminated n-undecanethiolate; denoted as SC11BIPY) is systematically diluted with nonrectifying n-alkanethiolates of different lengths (denoted as SC n where n = 8, 10, 12, 14, 16, 18). Characterization of the resulting mixed SAMs in wettability and tunneling currents with the two separate liquid top-contacts allows us to investigate the role of phase segregation and gauche defect in the SAM//liquid interfaces. The results reported here show the difference in length between SC11BIPY and SC n is translated into nanoscopic pits and gauche-conformer defects on the surface, and the difference in contact force-hydrostatic vs user pressures-and hence conformity of contact account for the difference in wettability and rectification behaviors. Our work provides an insight into the role of molecule-electrode interfacial defects in performance of molecular-scale electronic devices.

Deconvolution of Tunneling Current in Large-Area Junctions Formed with Mixed Self-Assembled Monolayers.

Whereas single-component self-assembled monolayers (SAMs) have served widely as organic components in molecular and organic electronics, how the performance of the device is influenced by the heterogeneity of monolayers has been little understood. This paper describes charge transport by quantum tunneling across mixed SAMs of n-alkanethiolates of different lengths formed on ultraflat template-stripped gold substrate. Electrical characterization using liquid metal comprising eutectic gallium-indium alloy reveals that the surface topography of monolayer largely depends on the difference in length between the thiolates and is translated into distribution of tunneling current density. As the length difference is more significant, more phase segregation takes place, leading to an increase in the modality of Gaussian fitting curves. Consequently, statistical analysis permits access to deconvolution of tunneling currents, mirroring the phase-segregated surface. Our work provides an insight into the role of surface topography in the performance of molecular-scale electronic devices.

Coherent Resonant Electron Tunneling at 9 and 300 K through a 4.5 nm Long, Rigid, Planar Organic Molecular Wire.

Organic molecular wires that operate stably at ambient temperatures are a necessary first step toward practical and useful molecular-scale electronic devices, which have thus far been hampered by many factors, including the structural and electron configurational instability of organic molecules. We report here that a single disulfanyl carbon-bridged oligo(phenylenevinylene) (COPV6) molecule embedded between thermally stable electroless Au-plated electrodes of a 4 nm nanogap undergoes coherent resonant tunneling at both 9 and 300 K and functions even after storage in air at room temperature. Such enormous stability is ascribed to the unique structural characteristics of COPV6, that is, rigidity, planarity, thermal stability, resistivity against oxidation and reduction, and an organic insulating sheath that protects the π-system. When sandwiched between the gaps without pinning, this molecule behaves as a Coulomb island with sequential single-electron tunneling at 9 K that disappears at 300 K while maintaining a stable electron flow.

Maskless Arbitrary Writing of Molecular Tunnel Junctions.

Since fabricating geometrically well-defined, noninvasive, and compliant electrical contacts over molecular monolayers is difficult, creating molecular-scale electronic devices that function in high yield with good reproducibility is challenging. Moreover, none of the previously reported methods to form organic-electrode contacts at the nanometer and micrometer scales have resulted in directly addressable contacts in an untethered form under ambient conditions without the use of cumbersome equipment and nanolithography. Here we show that in situ encapsulation of a liquid metal (eutectic Ga-In alloy) microelectrode, which is used for junction formation, with a convenient photocurable polymeric scaffold enables untethering of the electrode and direct writing of arbitrary arrays of high-yielding molecular junctions under ambient conditions in a maskless fashion. The formed junctions function in quantitative yields and can afford tunneling currents with high reproducibility; they also function at low temperatures and under bent. The results reported here promise a massively parallel printing technology to construct integrated circuits based on molecular junctions with soft top contacts.

Photodetection of Near and Middle IR Lasers by f-MWCNTs/Polythiophen Nanocomposite Detector

The combination of carbon nanotubes (CNT) and conducting polymers offers an attractive route for the production of novel compounds that can be used in a variety of applications such as sensors, actuators, and molecular scale electronic devices. In this work, functionalized multiwall carbon nanotubes (f-MWCNTs) were added in different load ratios (3 wt%, 5 wt% and 10 wt%) to thiophen (PTh) polymer to procedure PTh/CNTs nanocomposite and deposited on porous silicon substrate by electropolarization. Photoconductive detectors were fabricated using PTh/f-MWCNTs matrix to work in the near region and middle IR regions. These detectors were illuminated by semiconductor laser diode wavelength of 808(nm) and Nd-YAG laser of wavelength 1064 (nm) to study the I-V characteristics and figures of merit. FTIR spectra assignments verify that the thiophene groups were successfully introduced into the carbon nanotubes. SEM images reflect that the electro polymerization process gives well coating for the CNTs by PTh. The conductivity of PTh as a function of temperature increased about 30 times due to addition of f-MWCNTs. Figures of merit reflect a good IR radiation sensitivity and photo response. The specific detectivity was in order of 108 (cm.Hz1/2/W) for both IR regions. The rise and fall times of the output signal are about of 192 (μs) and 121 (μs) respectively for load ratio 5wt% of CNT, which consider good values for these types of detectors.

Effect of surface passivation on breakdown voltages of 4H-SiC Schottky barrier diodes

In this study, we fabricated and characterized graphene/molecule/graphene (GMG) vertical junctions with aryl alkane monolayers. The constituent molecules were chemically self-assembled via electrophilic diazonium reactions into a monolayer on the graphene bottom electrode, while the other end physically contacted the graphene top electrode. A full understanding of the transport properties of molecular junctions is a key step in the realization of molecular-scale electronic devices and requires detailed microscopic characterization of the junction’s active region. Using a multiprobe approach combining a variety of transport techniques, we elucidated the transport mechanisms and electronic structure of the GMG junctions, including temperature- and length-variable transport measurements, and transition voltage spectroscopy. These results provide criteria to establish a valid molecular junction and to determine the most probable transport characteristics of the GMG junctions.

Motion of Fullerenes around Topological Defects on Metals: Implications for the Progress of Molecular Scale Devices.

Research on motion of molecules in the presence of thermal noise is central for progress in two-terminal molecular scale electronic devices. However, it is still unclear what influence imperfections in bottom metal electrode surface can have on molecular motion. Here, we report a two-layer crowding study, detailing the early stages of surface motion of fullerene molecules on Au(111) with nanoscale pores in a n-tetradecane chemical environment. The motion of the fullerenes is directed by crowding of the underlying n-tetradecane molecules around the pore fringes at the liquid-solid interface. We observe in real-space the growth of molecular populations around different pore geometries. Supported by atomic-scale modeling, our findings extend the established picture of molecular crowding by revealing that trapped solvent molecules serve as prime nucleation sites at nanopore fringes.

Modulation and Control of Charge Transport Through Single-Molecule Junctions.

The ability to modulate and control charge transport though single-molecule junction devices is crucial to achieving the ultimate goal of molecular electronics: constructing real-world-applicable electronic components from single molecules. This review aims to highlight the progress made in single-molecule electronics, emphasizing the development of molecular junction electronics in recent years. Among many techniques that attempt to wire a molecule to metallic electrodes, the single-molecule break junction (SMBJ) technique is one of the most reliable and tunable experimental platforms for achieving metal-molecule-metal configurations. It also provides great freedom to tune charge transport through the junction. Soon after the SMBJ technique was introduced, it was extensively used to measure the conductances of individual molecules; however, different conductances were obtained for the same molecule, and it proved difficult to interpret this wide distribution of experimental data. This phenomenon was later found to be mainly due to a lack of precise experimental control and advanced data analysis methods. In recent years, researchers have directed considerable effort into advancing the SMBJ technique by gaining a deeper physical understanding of charge transport through single molecules and thus enhancing its potential applicability in functional molecular-scale electronic devices, such as molecular diodes and molecular transistors. In parallel with that research, novel data analysis methods and approaches that enable the discovery of hidden yet important features in the data are being developed. This review discusses various aspects of molecular junction electronics, from the initial goal of molecular electronics, the development of experimental techniques for creating single-molecule junctions and determining single-molecule conductance, to the characterization of functional current-voltage features and the investigation of physical properties other than charge transport. In addition, the development of advanced data analysis methods is considered, as they are critical to gaining detailed physical insight into the underlying transport mechanisms.