Single‐Molecule Devices: Single Molecule Electronic Devices (Adv. Mater. 14/2011)

Single molecule electronic devices in which individual molecules are utilized as active electronic components constitute a promising approach for the ultimate miniaturization and integration of electronic devices in nanotechnology through the bottom‐up strategy. Thus, the ability to understand, control, and exploit charge transport at the level of single molecules has become a long‐standing desire of scientists and engineers from different disciplines for various potential device applications. Indeed, a study on charge transport through single molecules attached to metallic electrodes is a very challenging task, but rapid advances have been made in recent years. This review article focuses on experimental aspects of electronic devices made with single molecules, with a primary focus on the characterization and manipulation of charge transport in this regime.     

Controlling Electronic States and Transport Properties at the Level of Single Molecules

Since molecular electronics has been rapidly growing as a promising alternative to conventional electronics towards the ultimate miniaturization of electronic devices through the bottom‐up strategy, it has become a long‐term desire to understand and control the transport properties at the level of single molecules. In this Research News article it is shown that one may modify the electronic states of single molecules and thus control their transport properties through designing and fabrication of functional molecules or manipulating molecules with scanning tunneling microscopy. The rectifying effect of single molecules can be realized by designing a donor–barrier–acceptor architecture of Pyridine–σ–C₆₀ molecules to achieve the Aviram–Ratner rectifier and by modifying electronic states through azafullerene C₅₉N molecules. The effect of the negative differential resistances can be realized by appropriately matching the molecular orbital symmetries between a cobalt phthalocyanine (CoPc) molecule and a Ni electrode. The electronic states and transport properties of single molecules, such as CoPc and melamine molecules, can be altered through manipulation or modifying molecular structures, leading to functionalized molecular devices.     

Tuning the Optical and Electrical Properties of Few‐Layer Black Phosphorus via Physisorption of Small Solvent Molecules

Black phosphorus (BP) is recently becoming more and more popular among semiconducting 2D materials for (opto)electronic applications. The controlled physisorption of molecules on the BP surface is a viable approach to modulate its optical and electronic properties. Solvents consisting of small molecules are often used for washing 2D materials or as liquid media for their chemical functionalization with larger molecules, disregarding their ability to change the opto‐electronic properties of BP. Herein, it is shown that the opto‐electronic properties of mechanically exfoliated few‐layer BP are altered when physically interacting with common solvents. Significantly, charge transport analysis in field‐effect transistors reveals that physisorbed solvent molecules induce a modulation of the charge carrier density which can be as high as 10¹² cm^?2 in BP, i.e., comparable to common dopants such as F₄‐TCNQ and MoO₃. By combining experimental evidences with density functional theory calculations, it is confirmed that BP doping by solvent molecules not only depends on charge transfer, but is also influenced by molecular dipole. The results clearly demonstrate how an exquisite tuning of the opto‐electronic properties of few‐layer BP can be achieved through physisorption of small solvent molecules. Such findings are of interest both for fundamental studies and more technological applications in opto‐electronics.     

Nanoparticle Linker‐Controlled Molecular Wire Devices Based on Double Molecular Monolayers

Highly conductive molecular wires are an important component for realizing molecular electronic devices and have to be explored in terms of interactions between molecules and electrodes in their molecular junctions. Here, new molecular wire junctions are reported to enhance charge transport through gold nanoparticle (AuNP)‐linked double self‐assembled monolayers (SAMs) of cobalt (II) bis‐terpyridine molecules (e.g., Co(II)(tpyphS)₂). Electrical characteristics of the double‐SAM devices are explored in terms of the existence of AuNP. The AuNP linker in the Co(II)(tpyphS)₂–AuNP–Co(II)(tpyphS)₂ junction acts as an electronic contact that is transparent to electrons. The weak temperature dependency of the AuNP‐linked molecular junctions strongly indicates sequential tunneling conduction through the highest occupied molecular orbitals (HOMOs) of Co(II)(tpyphS)₂ molecules. The electrochemical characteristics of the AuNP–Co(II)(tpyphS)₂ SAMs reveal fast electron transfer through molecules linked by AuNP. Density functional theory calculations reveal that the molecular HOMO levels are dominantly affected by the formation of junctions. The intermolecular charge transport, controlled by the AuNP linker, can provide a rational design for molecular connection that achieves a reliable electrical connectivity of molecular electronic components for construction of molecular electronic circuits.     

Effects of electric field and charge distribution on nanoelectronic processes involving conducting polymers

The injection of charge carriers in conducting polymer layers gives rise to local electric fields which should have serious implications on the charge transport through the polymer layer. The charge distribution and the related electric field inside the ensemble of polymer molecules, with different molecular arrangements at nanoscale, determine whether or not intra-molecular charge transport takes place and the preferential direction for charge hopping between neighbouring molecules. Consequently, these factors play a significant role in the competition between current flow, charge trapping and recombination in polymer-based electronic devices. By suitable Monte Carlo calculations, we simulated the continuous injection of electrons and holes into polymer layers with different microstructures and followed their transport through those polymer networks. Results of these simulations provided a detailed picture of charge and electric field distribution in the polymer layer and allowed us to assess the consequences for current transport and recombination efficiency as well as the distribution of recombination events within the polymer film. In the steady state we found an accumulation of electrons and holes near the collecting electrodes giving rise to an internal electric field which is greater than the external applied field close to the electrodes and lower than the one in the central region of the polymer layer. We also found that a strong variation of electric field inside the polymer layer leads to an increase of recombination events in regions inside the polymer layer where the values of the internal electric field are lower.     

Molecular junctions based on aromatic coupling

If individual molecules are to be used as building blocks for electronic devices, it will be essential to understand charge transport at the level of single molecules. Most existing experiments rely on the synthesis of functional rod-like molecules with chemical linker groups at both ends to provide strong, covalent anchoring to the source and drain contacts. This approach has proved very successful, providing quantitative measures of single-molecule conductance, and demonstrating rectification and switching at the single-molecule level. However, the influence of intermolecular interactions on the formation and operation of molecular junctions has been overlooked. Here we report the use of oligo-phenylene ethynylene molecules as a model system, and establish that molecular junctions can still form when one of the chemical linker groups is displaced or even fully removed. Our results demonstrate that aromatic pi-pi coupling between adjacent molecules is efficient enough to allow for the controlled formation of molecular bridges between nearby electrodes.     

Digital memory device based on tobacco mosaic virus conjugated with nanoparticles

Nanostructured viruses are attractive for use as templates for ordering quantum dots to make self-assembled building blocks for next-generation electronic devices. So far, only a few types of electronic devices have been fabricated from biomolecules due to the lack of charge transport through biomolecular junctions. Here, we show a novel electronic memory effect by incorporating platinum nanoparticles into tobacco mosaic virus. The memory effect is based on conductance switching, which leads to the occurrence of bistable states with an on/off ratio larger than three orders of magnitude. The mechanism of this process is attributed to charge trapping in the nanoparticles for data storage and a tunnelling process in the high conductance state. Such hybrid bio-inorganic nanostructures show promise for applications in future nanoelectronics.     

Modelling the effect of structure and base sequence on DNA molecular electronics

DNA is a material that has the potential to be used in nanoelectronic devices as an active component. However, the electronic properties of DNA responsible for its conducting behaviour remain controversial. Here we use a self-consistent quantum molecular dynamics method to study the effect of DNA structure and base sequence on the energy involved when electrons are added or removed from isolated molecules and the transfer of the injected charge along the molecular axis when an electric field is applied. Our results show that the addition or removal of an electron from DNA molecules is most exothermic for poly(dC)-poly(dG) in its B-form and poly(dA)-poly(dT) in its A-form, and least exothermic in its Z-form. Additionally, when an electric field is applied to a charged DNA molecule along its axis, there is electron transfer through the molecule, regardless of the number and sign of the injected charge, the molecular structure and the base sequence. Results from these simulations provide useful information that is hard to obtain from experiments and needs to be considered for further modelling aiming to improve charge transport efficiency in nanoelectronic devices based on DNA.     

Electron transport in molecular junctions

Building an electronic device using individual molecules is one of the ultimate goals in nanotechnology. To achieve this it will be necessary to measure, control and understand electron transport through molecules attached to electrodes. Substantial progress has been made over the past decade and we present here an overview of some of the recent advances. Topics covered include molecular wires, two-terminal switches and diodes, three-terminal transistor-like devices and hybrid devices that use various different signals (light, magnetic fields, and chemical and mechanical signals) to control electron transport in molecules. We also discuss further issues, including molecule-electrode contacts, local heating- and current-induced instabilities, stochastic fluctuations and the development of characterization tools.     

Transistor-like behavior of transition metal complexes

Electron transport through semiconductor and metallic nanoscale structures, molecular monolayers, and single molecules connected to external electrodes display rectification, switch, and staircase functionality of potential importance in future miniaturization of electronic devices. Common to most reported systems is, however, ultrahigh vacuum and/or cryogenic working conditions. Here we introduce a single-molecule device concept based on a class of robust redox active transition metal (Os(II)/(III)) complexes inserted between the working electrode and tip in an electrochemical scanning tunneling microscope (in situ STM). This configuration resembles a single-molecule transistor, where the reference electrode corresponds to the gate electrode. It operates at room temperature in a condensed matter (here aqueous) environment. Amplification on-off ratios up to 50 are found when the redox level is brought into the energy window between the Fermi levels of the electrodes by the overpotential ("gate voltage"). The current-voltage characteristics for two Os(II)/(III) complexes have been characterized systematically and supported by theoretical frames based on molecular charge transport theory.     

Electron Hopping Across Hemin‐Doped Serum Albumin Mats on Centimeter‐Length Scales

Exploring long‐range electron transport across protein assemblies is a central interest in both the fundamental research of biological processes and the emerging field of bioelectronics. This work examines the use of serum‐albumin‐based freestanding mats as macroscopic electron mediators in bioelectronic devices. In particular, this study focuses on how doping the protein mat with hemin improves charge‐transport. It is demonstrated that doping can increase conductivity 40‐fold via electron hopping between adjacent hemin molecules, resulting in the highest measured conductance for a protein‐based material yet reported, and transport over centimeter length scales. The use of distance‐dependent AC impedance and DC current–voltage measurements allows the contribution from electron hopping between adjacent hemin molecules to be isolated. Because the hemin‐doped serum albumin mats have both biocompatibility and fabrication simplicity, they should be applicable to a range of bioelectronic devices of varying sizes, configurations, and applications.     

Solar cells with graphene and carbon nanotubes on silicon

Graphene and carbon nanotubes (CNTs) represent attractive materials for photovoltaic (PV) devices due to their unique electronic and optical properties. Graphene and single-wall carbon nanotubes (SWNTs) layers can be directly configured as energy conversion materials to fabricate thin-film solar cells, serving as both photogeneration sites and charge carrier collecting/transport layers. SWNTs can be modified into either p-type conductor through chemical doping (like acidic purification) or n-type conductor through polymer functionalisation. The solar cells can be simply made of a semitransparent thin film of graphene (or SWNTs) deposited on a proper type of silicon substrate to create high-density Schottky (or p–n) junctions at the interface. The high aspect ratios and large surface area of these carbon nano-structured materials can benefit exciton dissociation and charge carrier transport thus improving the power conversion efficiency.     

Single-crystal organic charge-transfer interfaces probed using Schottky-gated heterostructures

Organic semiconductors based on small conjugated molecules generally behave as insulators when undoped, but the heterointerfaces of two such materials can show electrical conductivity as large as in a metal. Although charge transfer is commonly invoked to explain the phenomenon, the details of the process and the nature of the interfacial charge carriers remain largely unexplored. Here we use Schottky-gated heterostructures to probe the conducting layer at the interface between rubrene and PDIF-CN(2) single crystals. Gate-modulated conductivity measurements demonstrate that interfacial transport is due to electrons, whose mobility exhibits band-like behaviour from room temperature to ~150 K, and remains as high as ~1 cm(2) V(-1) s(-1) at 30 K for the best devices. The electron density decreases linearly with decreasing temperature, an observation that can be explained quantitatively on the basis of the heterostructure band diagram. These results elucidate the electronic structure of rubrene/PDIF-CN(2) interfaces and show the potential of Schottky-gated organic heterostructures for the investigation of transport in molecular semiconductors.     

Coherent single charge transport in molecular-scale silicon nanowires

We report low-temperature electrical transport studies of chemically synthesized, molecular-scale silicon nanowires. Individual nanowires exhibit Coulomb blockade oscillations characteristic of charge addition to a single nanostructure on length scales up to at least 400 nm. Studies also demonstrate coherent charge transport through discrete single particle quantum levels extending across whole devices, and show that the ground-state spin configuration is consistent with the constant interaction model. In addition, depletion of nanowires suggests that phase coherent single-dot characteristics are accessible in the few-charge regime. These results differ from those for nanofabricated planar silicon devices, which show localization on much shorter length scales, and thus suggest potential for molecular-scale silicon nanowires as building blocks for quantum and conventional electronics.     

Field-effect-modulated Seebeck coefficient in organic semiconductors

Central to the operation of organic electronic and optoelectronic devices is the transport of charge and energy in the organic semiconductor, and to understand the nature and dynamics of charge carriers is at the focus of intense research efforts. As a basic transport property of solids, the Seebeck coefficient S provides deep insight as it is given by the entropy transported by thermally excited charge carriers and involves in the simplest case only electronic contributions where the transported entropy is determined by details of the band structure and scattering events. We have succeeded for the first time to measure the temperature- and carrier-density-dependent thermopower in single crystals and thin films of two prototypical organic semiconductors by a controlled modulation of the chemical potential in a field-effect geometry. Surprisingly, we find the Seebeck coefficient to be well within the range of the electronic contribution in conventional inorganic semiconductors, highlighting the similarity of transport mechanisms in organic and inorganic semiconductors. Charge and entropy transport is best described as band-like transport of quasiparticles that are subjected to scattering, with exponentially distributed in-gap trap states, and without further contributions to S.     

Effects of hydration on molecular junction transport

The study of charge transport through increasingly complex small molecules will benefit from a detailed understanding of how contaminants from the environment affect molecular conduction. This should provide a clearer picture of the electronic characteristics of molecules by eliminating interference from adsorbed species. Here we use magnetically assembled microsphere junctions incorporating thiol monolayers to provide insight into changing electron transport characteristics resulting from exposure to air. Using this technique, current-voltage analysis and inelastic electron tunnelling spectroscopy (IETS) demonstrate that the primary interaction affecting molecular conduction is rapid hydration at the gold-sulphur contacts. We use IETS to present evidence for changing mechanisms of charge transport as a result of this interaction. The detrimental effects on molecular conduction discussed here are important for understanding electron transport through gold-thiol molecular junctions once exposed to atmospheric conditions.     

Probing molecules in integrated silicon-molecule-metal junctions by inelastic tunneling spectroscopy

Molecular electronics has drawn significant attention for nanoelectronic and sensing applications. A hybrid technology where molecular devices are integrated with traditional semiconductor microelectronics is a particularly promising approach for these applications. Key challenges in this area include developing devices in which the molecular integrity is preserved, developing in situ characterization techniques to probe the molecules within the completed devices, and determining the physical processes that influence carrier transport. In this study, we present the first experimental report of inelastic electron tunneling spectroscopy of integrated metal-molecule-silicon devices with molecules assembled directly to silicon contacts. The results provide direct experimental confirmation that the chemical integrity of the monolayer is preserved and that the molecules play a direct role in electronic conduction through the devices. Spectra obtained under varying measurement conditions show differences related to the silicon electrode, which can provide valuable information about the physics influencing carrier transport in these molecule/Si hybrid devices.     

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.     

Mechanically Controllable Break Junctions for Molecular Electronics

A mechanically controllable break junction (MCBJ) represents a fundamental technique for the investigation of molecular electronic junctions, especially for the study of the electronic properties of single molecules. With unique advantages, the MCBJ technique has provided substantial insight into charge transport processes in molecules. In this review, the techniques for sample fabrication, operation and the various applications of MCBJs are introduced and the history, challenges and future of MCBJs are discussed.     

Flexible molecular-scale electronic devices

Flexible materials and devices could be exploited in light-emitting diodes, electronic circuits, memory devices, sensors, displays, solar cells and bioelectronic devices. Nanoscale elements such as thin films, nanowires, nanotubes and nanoparticles can also be incorporated into the active films of mechanically flexible devices. Large-area devices containing extremely thin films of molecular materials represent the ultimate scaling of flexible devices based on organic materials, but the influence of bending and twisting on the electrical and mechanical stability of such devices has never been examined. Here, we report the fabrication and characterization of two-terminal electronic devices based on self-assembled monolayers of alkyl or aromatic thiol molecules on flexible substrates. We find that the charge transport characteristics of the devices remain stable under severe bending conditions (radius?≤?1?mm) and a large number of repetitive bending cycles (≥1,000). The devices also remain reliable in various bending configurations, including twisted and helical structures.