Electromechanical and conductance switching properties of single oligothiophene molecules

We have studied the electron transport and electromechanical properties of single oligothiophenes with three and four thiophene repeating units covalently linked to two Au electrodes. The four-repeating unit molecule is found to be more conductive than the three-repeating unit molecule. This unusual length dependence is due to the different electronic states of the molecules. Both molecules can be switched reversibly between a high and low conducting state by oxidizing and reducing the molecules using an electrochemical gate. The conductance of the molecules decreases upon stretching, which is attributed to a force-induced increase in the HOMO-LUMO gap.     

Low-bias conductance of single benzene molecules contacted by direct Au-C and Pt-C bonds

The electronic transport properties of a single benzene molecule connected to gold and platinum electrodes through the direct Au-C or Pt-C bond are investigated by using a self-consistent ab initio approach that combines the non-equilibrium Green's function (NEGF) formalism with density functional theory (DFT). Our calculations show that the benzene molecule can bind to the Au(111) surface via direct Au-C bond at the adatom, atop and bridge sites. The largest zero-bias conductance is calculated for the bridge site but it is only G = 0.37G(0) (G(0) = 2e(2)/h). In contrast benzene binds to the Pt(111) surface via direct Pt-C bond only at the adatom and atop sites. When the binding site is the adatom a stable molecular junction forms with a zero-bias conductance as large as 1.15G(0). This originates from the efficient coupling between the extended π-type highest occupied molecular orbital of benzene and the conducting states of the Pt electrodes via the 5d(xz) atomic orbital of the adatoms. The calculated transmission is robust to the choice of DFT functionals, illustrating the potential of the Pt-C bond for constructing future molecular electronic devices.     

Mechanism of conductance switching: An optical investigation

Electronic conductance switching in devices based on thin films of an organic molecule has been studied. Switching between two conducting states has been induced by voltage pulse, while the states have been probed by optical and electrical measurements simultaneously. In situ optical measurements showed that electroreduction of molecules led to conductance switching and appearance of high-conducting state in the device. We could “write” or “erase” a state by applying electrical pulse and “read” it by measuring electronic absorbance and conductivity. The “write” and “read” processes have been carried out for many cycles to exhibit a correspondence between conductance switching and electrochromism.     

Reversible Ion‐Conducting Switch in a Novel Single‐Ion Supramolecular Hydrogel Enabled by Photoresponsive Host–Guest Molecular Recognition

A novel ion‐conducting supramolecular hydrogel with reversible photoconductive properties in which the azobenzene motif, α‐cyclodextrin (α‐CD), and ionic liquid are grafted onto the gel matrix is reported. Host–guest interactions with different association constants between α‐CD and azobenzene or the anionic part of the ionic liquid can be readily tuned by photoinduced trans–cis isomerization of the azobenzene unit. When irradiated by 365 nm light, α‐CD prefers to form a complex with the anionic part of the ionic liquid, resulting in decreased ionic mobility and thus high resistance of the hydrogel. However, under 420 nm light irradiation, a more stable complex is again formed between α‐CD and trans‐azobenzene, thereby releasing the bound anions to regenerate the low‐resistive hydrogel. As such, remote control of the ionic conductivity of the hydrogel is realized by simple host–guest chemistry. With the incorporation of a logic gate, this hydrogel is able to reversibly switch an electric circuit on and off by light irradiation with certain wavelengths. The concept of photoswitchable ionic conductivity of a hydrogel mediated by competitive molecular recognition is potentially promising toward the fabrication of optoelectronic devices and applications in bioelectronic technology.     

Strongly Correlated Aromatic Molecular Conductor

Strongly correlated electronic molecules open the way for strong coupling between charge, spin, and lattice degrees of freedom to enable interdisciplinary fields, such as molecular electronic switches and plasmonics, spintronics, information storage, and superconducting circuits. However, despite exciting computational predictions and promising advantages to prepare flexible geometries, the electron correlation effect in molecules has been elusive. Here, the electron correlation effects of molecular plasmonic films are reported to uncover their coupling of charge, spin, lattice, and orbital for the switchable metal‐to‐insulator transition under external stimuli, at which the simultaneous transition occurs from the paramagnetic, electrical, and thermal conducting state to the diamagnetic, electrical, and thermal insulating state. In addition, density functional theory calculation and spectroscopic studies are combined to provide the mechanistic understanding of electronic transitions and molecular plasmon resonance observed in molecular conducting films. The self‐assembled molecular correlated conductor paves the way for the next generation integrated micro/nanosystems.     

Switchable ternary nanoporous supramolecular network on photo-regulation

Controlled regulation of the switchable behavior of the supramolecular network is central to the potential application in the molecular scale nanodevices. In this work, it is reported that the reversible accommodation of the guest molecules in the nanoporous supramolecular network can be regulated by the UV/visible light. The nanoporous complex template of TCDB/4NN-Macrocycle(trans,trans,trans,trans) with photosensitive units is well-defined. After the UV irradiation, the template can be switched on to encapsulate coronene molecules due to the formation of a new photoisomer(trans,cis,trans,cis) and switched off to expel coronene from the inner cavities under the visible light. The photoregulated switchable multicomponent supramolecular guest-host network provides a novel strategy for fabricating the functional nanodevices at the molecular scale.     

Gate‐Tunable and Multidirection‐Switchable Memristive Phenomena in a Van Der Waals Ferroelectric

Memristive devices have been extensively demonstrated for applications in nonvolatile memory, computer logic, and biological synapses. Precise control of the conducting paths associated with the resistance switching in memristive devices is critical for optimizing their performances including ON/OFF ratios. Here, gate tunability and multidirectional switching can be implemented in memristors for modulating the conducting paths using hexagonal α‐In₂Se₃, a semiconducting van der Waals ferroelectric material. The planar memristor based on in‐plane (IP) polarization of α‐In₂Se₃ exhibits a pronounced switchable photocurrent, as well as gate tunability of the channel conductance, ferroelectric polarization, and resistance‐switching ratio. The integration of vertical α‐In₂Se₃ memristors based on out‐of‐plane (OOP) polarization is demonstrated with a device density of 7.1 × 10⁹ in.^?2 and a resistance‐switching ratio of well over 10³. A multidirectionally operated α‐In₂Se₃ memristor is also proposed, enabling the control of the OOP (or IP) resistance state directly by an IP (or OOP) programming pulse, which has not been achieved in other reported memristors. The remarkable behavior and diverse functionalities of these ferroelectric α‐In₂Se₃ memristors suggest opportunities for future logic circuits and complex neuromorphic computing.     

Mechanism of conductance switching: An optical investigation

Electronic conductance switching in devices based on thin films of an organic molecule has been studied. Switching between two conducting states has been induced by voltage pulse, while the states have been probed by optical and electrical measurements simultaneously. In situ optical measurements showed that electroreduction of molecules led to conductance switching and appearance of high-conducting state in the device. We could “write” or “erase” a state by applying electrical pulse and “read” it by measuring electronic absorbance and conductivity. The “write” and “read” processes have been carried out for many cycles to exhibit a correspondence between conductance switching and electrochromism.     

Multiphotoluminescence from a Triphenylamine Derivative and Its Application in White Organic Light‐Emitting Diodes Based on a Single Emissive Layer

White organic light‐emitting diode (WOLED) technology has attracted considerable attention because of its potential use as a next‐generation solid‐state lighting source. However, most of the reported WOLEDs that employ the combination of multi‐emissive materials to generate white emission may suffer from color instability, high material cost, and a complex fabrication procedure which can be diminished by the single‐emitter‐based WOLED. Herein, a color‐tunable material, tris(4‐(phenylethynyl)phenyl)amine (TPEPA), is reported, whose photoluminescence (PL) spectrum is altered by adjusting the thermal annealing temperature nearly encompassing the entire visible spectra. Density functional theory calculations and transmission electron microscopy results offer mechanistic understanding of the PL redshift resulting from thermally activated rotation of benzene rings and rotation of 4‐(phenylethynyl) phenyl)amine connected to the central nitrogen atom that lead to formation of ordered molecular packing which improves the π–π stacking degree and increases electronic coupling. Further, by precisely controlling the annealing time and temperature, a white‐light OLED is fabricated with the maximum external quantum efficiency of 3.4% with TPEPA as the only emissive molecule. As far as it is known, thus far, this is the best performance achieved for single small organic molecule based WOLED devices.     

Optical modulation of molecular conductance

A novel scanning probe microscope stage permits break junction measurements of single molecule conductance while the molecules are illuminated with visible light. We studied a porphyrin-fullerene dyad molecule designed to form a charge separated state on illumination. A significant fraction of illuminated molecules become more conductive, returning to a lower conductance in the dark, suggesting the formation of a long-lived charge separated state on the indium-tin oxide surface. Transient absorption spectra of these molecular layers are consistent with formation of a long-lived charge separated state, a finding with implications for the design of molecular photovoltaic devices.     

Assembling molecular electronic junctions one molecule at a time

Diffusion of metal atoms onto a molecular monolayer attached to a conducting surface permits electronic contact to the molecules with minimal heat transfer or structural disturbance. Surface-mediated metal deposition (SDMD) involves contact between "cold" diffusing metal atoms and molecules, due to shielding of the molecules from direct exposure to metal vapor. Measurement of the current through the molecular layer during metal diffusion permits observation of molecular conductance for junctions containing as few as one molecule. Discrete conductance steps were observed for 1-10 molecules within a monolayer during a single deposition run, corresponding to "recruitment" of additional molecules as the contact area between the diffusing Au layer and molecules increases. For alkane monolayers, the molecular conductance measured with SDMD exhibited an exponential dependence on molecular length with a decay constant (β) of 0.90 per CH(2) group, comparable to that observed by other techniques. Molecular conductance values were determined for three azobenzene molecules, and correlated with the offset between the molecular HOMO and the contact Fermi level, as expected for hole-mediated tunneling. Current-voltage curves were obtained during metal deposition showed no change in shape for junctions containing 1, 2, and 10 molecules, implying minimal intermolecular interactions as single molecule devices transitioned into several molecules devices. SDMD represents a "soft" metal deposition method capable of providing single molecule conductance values, then providing quantitative comparisons to molecular junctions containing 10(6) to 10(10) molecules.     

Progress with Molecular Electronic Junctions: Meeting Experimental Challenges in Design and Fabrication

Molecular electronics seeks to incorporate molecular components as functional elements in electronic devices. There are numerous strategies reported to date for the fabrication, design, and characterization of such devices, but a broadly accepted example showing structure‐dependent conductance behavior has not yet emerged. This progress report focuses on experimental methods for making both single‐molecule and ensemble molecular junctions, and highlights key results from these efforts. Based on some general objectives of the field, particular experiments are presented to show progress in several important areas, and also to define those areas that still need attention. Some of the variable behavior of ostensibly similar junctions reported in the literature is attributable to differences in the way the junctions are fabricated. These differences are due, in part, to the multitude of methods for supporting the molecular layer on the substrate, including methods that utilize physical adsorption and covalent bonds, and to the numerous strategies for making top contacts. After discussing recent experimental progress in molecular electronics, an assessment of the current state of the field is presented, along with a proposed road map that can be used to assess progress in the future.     

Electrical Tunability of Domain Wall Conductivity in LiNbO3 Thin Films

Domain wall nanoelectronics is a rapidly evolving field, which explores the diverse electronic properties of the ferroelectric domain walls for application in low‐dimensional electronic systems. One of the most prominent features of the ferroelectric domain walls is their electrical conductivity. Here, using a combination of scanning probe and scanning transmission electron microscopy, the mechanism of the tunable conducting behavior of the domain walls in the sub‐micrometer thick films of the technologically important ferroelectric LiNbO₃ is explored. It is found that the electric bias generates stable domains with strongly inclined domain boundaries with the inclination angle reaching 20° with respect to the polar axis. The head‐to‐head domain boundaries exhibit high conductance, which can be modulated by application of the sub‐coercive voltage. Electron microscopy visualization of the electrically written domains and piezoresponse force microscopy imaging of the very same domains reveals that the gradual and reversible transition between the conducting and insulating states of the domain walls results from the electrically induced wall bending near the sample surface. The observed modulation of the wall conductance is corroborated by the phase‐field modeling. The results open a possibility for exploiting the conducting domain walls as the electrically controllable functional elements in the multilevel logic nanoelectronics devices.     

Nanolattices of Switchable DNA‐Based Motors

Miniaturization is an important aspect of device fabrication. Despite the advancements of modern top‐down approaches, scaling‐down to the sub‐nanometer size is still a challenge. As an alternative, bottom‐up approaches, such as the use of DNA as an engineering material, are therefore emerging, allowing control of matter at the single‐molecule level. A DNA‐based self‐assembly method for the construction of switchable DNA devices is descrbied here based on G‐quadruplex moieties, which are patterned on quasi‐planar DNA arrays with nanoscale precision. The reversible switching of the devices is triggered by addition of DNA sequences (‘fuels’) and translated into linear extension/contractile movements. The conformational change of the devices was visualized by atomic force microscopy and FRET spectroscopy. Steady state fluorescence spectroscopy indicated that scaffolding of the G4 motors to either individual tiles or extended superlattices had no significant impact on the switching and optical performance of the system. However, time‐resolved spectroscopy revealed that ordering in the microstructural environment enhances the fraction of molecules subject to FRET. Altogether, our study confirms that DNA superstructures are well‐suited scaffolds for accommodation of mechanically switchable units and thus opens the door to the development of more sophisticated nanomechanical devices.     

Self‐Assembled Monolayer Transistors

Self‐assembled monolayers of organic, conjugated molecules can be used as active components of field‐effect transistors. The length of the molecule can define critical device dimensions with high precision on the nanometer scale. Transistor effects on the molecular‐scale as well as in devices consisting of single active molecules have been demonstrated. The observed device performance indicates that such transistors might be useful for switching and amplifying electrical signals in logic circuits. Moreover, functionalizing the organic molecules reveals that different parts of the molecule can act as gate insulator or the active component of transistors. Such research might pave the way to molecular electronic applications.     

Nanogap Electrodes towards Solid State Single‐Molecule Transistors

With the establishment of complementary metal‐oxide‐semiconductor (CMOS)‐based integrated circuit technology, it has become more difficult to follow Moore's law to further downscale the size of electronic components. Devices based on various nanostructures were constructed to continue the trend in the minimization of electronics, and molecular devices are among the most promising candidates. Compared with other candidates, molecular devices show unique superiorities, and intensive studies on molecular devices have been carried out both experimentally and theoretically at the present time. Compared to two‐terminal molecular devices, three‐terminal devices, namely single‐molecule transistors, show unique advantages both in fundamental research and application and are considered to be an essential part of integrated circuits based on molecular devices. However, it is very difficult to construct them using the traditional microfabrication techniques directly, thus new fabrication strategies are developed. This review aims to provide an exclusive way of manufacturing solid state gated nanogap electrodes, the foundation of constructing transistors of single or a few molecules. Such single‐molecule transistors have the potential to be used to build integrated circuits.     

Three-terminal devices to examine single-molecule conductance switching

We report electronic transport measurements of single-molecule transistor devices incorporating bipyridyl-dinitro oligophenylene-ethynylene dithiol (BPDN-DT), a molecule known to exhibit conductance switching in other measurement configurations. We observe hysteretic conductance switching in 8% of devices with measurable currents and find that dependence of the switching properties on gate voltage is rare when compared to other single-molecule transistor devices. This suggests that polaron formation is unlikely to be responsible for switching in these devices. We discuss this and alternative switching mechanisms.     

A surface-anchored molecular four-level conductance switch based on single proton transfer

The development of a variety of nanoscale applications requires the fabrication and control of atomic or molecular switches that can be reversibly operated by light, a short-range force, electric current or other external stimuli. For such molecules to be used as electronic components, they should be directly coupled to a metallic support and the switching unit should be easily connected to other molecular species without suppressing switching performance. Here, we show that a free-base tetraphenyl-porphyrin molecule, which is anchored to a silver surface, can function as a molecular conductance switch. The saddle-shaped molecule has two hydrogen atoms in its inner cavity that can be flipped between two states with different local conductance levels using the electron current through the tip of a scanning tunnelling microscope. Moreover, by deliberately removing one of the hydrogens, a four-level conductance switch can be created. The resulting device, which could be controllably integrated into the surrounding nanoscale environment, relies on the transfer of a single proton and therefore contains the smallest possible atomistic switching unit.     

Construction of a Fuzzy and Boolean Logic Gates Based on DNA

Logic gates are devices that can perform logical operations by transforming a set of inputs into a predictable single detectable output. The hybridization properties, structure, and function of nucleic acids can be used to make DNA‐based logic gates. These devices are important modules in molecular computing and biosensing. The ideal logic gate system should provide a wide selection of logical operations, and be integrable in multiple copies into more complex structures. Here we show the successful construction of a small DNA‐based logic gate complex that produces fluorescent outputs corresponding to the operation of the six Boolean logic gates AND, NAND, OR, NOR, XOR, and XNOR. The logic gate complex is shown to work also when implemented in a three‐dimensional DNA origami box structure, where it controlled the position of the lid in a closed or open position. Implementation of multiple microRNA sensitive DNA locks on one DNA origami box structure enabled fuzzy logical operation that allows biosensing of complex molecular signals. Integrating logic gates with DNA origami systems opens a vast avenue to applications in the fields of nanomedicine for diagnostics and therapeutics.     

Alkali‐Metal‐Intercalated Percolation Network Regulates Self‐Assembled Electronic Aromatic Molecules

In the continuously growing field of correlated electronic molecular crystals, there is significant interest in addressing alkali‐metal‐intercalated aromatic hydrocarbons, in which the possibility of high‐temperature superconductivity emerges. However, searching for superconducting aromatic molecular crystals remains elusive due to their small shielding fraction volume. To exploit this potential, a design principle for percolation networks of technologically important film geometry is indispensable. Here the effect of potassium‐intercalation is shown on the percolation network in self‐assembled aromatic molecular crystals. It is demonstrated that one‐dimensional (1D) dipole pairs, induced by dipole interaction, regulate the conductivity, as well as the electronic and optical transitions, in alkali‐metal‐intercalated molecular electronic crystals. A solid‐solution growth methodology of aromatic molecular films with a broad range of stability is developed to uncover electronic and optical transitions of technological importance. The light‐induced electron interactions enhance the charge‐carrier itinerancy, leading to a switchable metal‐to‐insulator transition. This discovery opens a route for the development of aromatic molecular electronic solids and long‐term modulation of electronic efficacy in nanotechnologically important thin films.