Electron-beam evaporated silicon as a top contact for molecular electronic device fabrication

This paper discusses the electronic properties of molecular devices made using covalently bonded molecular layers on carbon surfaces with evaporated silicon top contacts. The Cu "top contact" of previously reported carbon/molecule/Cu devices was replaced with e-beam deposited Si in order to avoid Cu oxidation or electromigration, and provide further insight into electron transport mechanisms. The fabrication and characterization of the devices is detailed, including a spectroscopic assessment of the molecular layer integrity after top contact deposition. The electronic, optical, and structural properties of the evaporated Si films are assessed in order to determine the optical gap, work function, and film structure, and show that the electron beam evaporated Si films are amorphous and have suitable conductivity for molecular junction fabrication. The electronic characteristics of Si top contact molecular junctions made using different molecular layer structures and thicknesses are used to evaluate electron transport in these devices. Finally, carbon/molecule/silicon devices are compared to analogous carbon/molecule/metal junctions and the possible factors that control the conductance of molecular devices with differing contact materials are discussed.     

Organic electrodes based on grafted oligothiophene units in ultrathin, large-area molecular junctions

Molecular junctions were fabricated with the combined use of electrochemistry and conventional CMOS tools. They consist of a 5-10 nm thick layer of oligo(1-(2-bisthienyl)benzene) between two gold electrodes. The layer was grafted onto the bottom electrode using diazonium electroreduction, which yields a stable and robust gold-oligomer interface. The top contact was obtained by direct electron-beam evaporation on the molecular layers through masks defined by electron-beam lithography. Transport mechanisms across such easily p-dopable layers were investigated by analysis of current density-voltage (J-V) curves. Application of a tunneling model led to a transport parameter (thickness of ~2.4 nm) that was not consistent with the molecular thickness measured using AFM (~7 nm). Furthermore, for these layers with thicknesses of 5-10 nm, asymmetric J-V curves were observed, with current flowing more easily when the grafted electrode was positively polarized. In addition, J-V experiments at two temperatures (4 and 300 K) showed that thermal activation occurs for such polarization but is not observed when the bias is reversed. These results indicate that simple tunneling cannot describe the charge transport in these junctions. Finally, analysis of the experimental results in term of "organic electrode" and redox chemistry in the material is discussed.     

Surfactant-free water-processable photoconductive all-carbon composite

Heterojunctions between different graphitic nanostructures, including fullerenes, carbon nanotubes and graphene-based sheets, have attracted significant interest for light to electrical energy conversion. Because of their poor solubility, fabrication of such all-carbon nanocomposites typically involves covalently linking the individual constituents or the extensive surface functionalization to improve their solvent processability for mixing. However, such strategies often deteriorate or contaminate the functional carbon surfaces. Here we report that fullerenes, pristine single walled carbon nanotubes, and graphene oxide sheets can be conveniently coassembled in water to yield a stable colloidal dispersion for thin film processing. After thermal reduction of graphene oxide, a solvent-resistant photoconductive hybrid of fullerene-nanotube-graphene was obtained with on-off ratio of nearly 6 orders of magnitude. Photovoltaic devices made with the all-carbon hybrid as the active layer and an additional fullerene block layer showed unprecedented photovoltaic responses among all known all-carbon-based materials with an open circuit voltage of 0.59 V and a power conversion efficiency of 0.21%. The ease of making such surfactant-free, water-processed, carbon thin films could lead to their wide applications in organic optoelectronic devices.     

单分子结的构筑及分子电导性质的测试

分子电子学已成为21世纪研究的热点. 通过将具有特定功能的分子连接在纳米尺度金属电极之间从而构筑包括分子导线、开关、整流器在内的各种分子尺度电子器件, 这引起了科学家们广泛的研究兴趣. 在分子电子学研究中, 构筑金属/分子/金属(MMM)分子结是研究分子器件中电子传输性质的关键. 尽管已经取得了很大的进展, 目前在纳米尺度下构筑稳定可靠的MMM分子结并测试单个分子的电学性质仍然面临很多挑战. 本文着重对单分子电学性质的测试技术和相关理论研究的最新进展以及存在的挑战做了概述.     

Molecular-scale electronics: From device fabrication to functionality

Device fabrication and functionality are two crucial aspects in molecular-scale electronics. Recent advancesin this field, including fabrication and application of nanogap electrodes, self-assembled monolayers and their functional devicesarehighlighted in this review paper.     

Annealing sequence dependent open-circuit voltage of inverted polymer solar cells attributable to interfacial chemical reaction between top electrodes and photoactive layers

The ability to laminate and delaminate top metal contacts during the processing and testing of inverted polymer solar cells has led us to uncover the peculiar dependence of their open-circuit voltage (V(oc)) on the annealing sequence. Specifically, thermally annealing inverted polymer solar cells having bulk-heterojunction photoactive layers after top electrode deposition above 100 °C leads to lower V(oc) compared to analogous devices with unannealed photoactive layers or photoactive layers that have been annealed prior to metal electrode deposition. This reduction in V(oc), however, can be reversed when the top electrodes are replaced. This observation is thus a strong indication that such changes in V(oc) with annealing sequence are manifestations of changes at the top electrode-photoactive layer interface, and not structural changes in the bulk of the photoactive layer. Electronic characterization conducted on the photoactive layers and metal contacts after dissection of the polymer solar cells via delamination suggests the reduction of V(oc) on thermal annealing in the presence of the metal top contacts to stem from an interfacial chemical reaction between the photoactive layers and the metal electrodes. This chemically generated interfacial layer is removed upon electrode delamination, effectively reverting the V(oc) to its original value prior to thermal annealing when the top electrodes are replaced.     

In situ Raman spectroscopy of bias-induced structural changes in nitroazobenzene molecular electronic junctions

Carbon/nitroazobenzene (NAB)/titanium/gold molecular electronic junctions with active thicknesses of 7-8 nm were constructed having partially transparent Ti/Au top contacts, which permitted in situ monitoring of molecular structure with Raman spectroscopy for applied biases between +3 and -3 V. Deposition of the Ti/Au top contacts resulted in spectral changes similar to those accompanying NAB reduction in a conventional spectroelectrochemical experiment. Upon application of +3 V (carbon relative to Ti), the spectrum indicated reoxidation of the NAB reduction product, and this redox cycle could be repeated at least three times. When a voltage excursion to -2 or -3 V occurred, the spectra indicated irreversible loss of the nitro group, and a dramatic but reversible decrease in Raman intensity over the entire shift range examined. Negative applied voltage causes formation of reduced NAB and a high oxidation state of titanium, while positive voltage forms oxidized NAB and injects electrons into the titanium oxide layer. The spectral changes were correlated with current/voltage curves in order to probe the mechanism of rectification and conductance switching reported previously. Overall, the combination of spectroscopic and voltammetric results implies a conduction mechanism involving both NAB and titanium oxide, possibly mediated by the injection of carriers into the semiconducting titanium oxide, or by reduction of an insulating titanium oxide to a more conductive form.     

Nb2O5 as a new electron transport layer for double junction polymer solar cells

Nb(2)O(5) as a new electron transport layer (ETL) was used for double junction polymer solar cells. The Nb(2)O(5) ETL was prepared by spin coating a Nb(2)O(5) sol-gel solution onto the active layer of the optical front subcell. The double junction devices using Nb(2)O(5) ETL exhibit an open circuit voltage (V(oc)) of 1.30 V, which is close to the sum of the s of the individual subcells. The current density-voltage (J-V) simulation showed that the double junction device performance using Nb(2)O(5) as ETL could be significantly increased by reducing the series resistance (R(se)) and matching the current densities of the individual subcells.     

Single‐Walled Carbon Nanotube Based Molecular Switch Tunnel Junctions

This article describes two‐terminal molecular switch tunnel junctions (MSTJs) which incorporate a semiconducting, single‐walled carbon nanotube (SWNT) as the bottom electrode. The nanotube interacts noncovalently with a monolayer of bistable, nondegenerate [2]catenane tetracations, self‐organized by their supporting amphiphilic dimyristoylphosphatidyl anions which shield the mechanically switchable tetracations from a two‐micrometer wide metallic top electrode. The resulting 0.002 μm² area tunnel junction addresses a nanometer wide row of ≈2000 molecules. Active and remnant current–voltage measurements demonstrated that these devices can be reconfigurably switched and repeatedly cycled between high and low current states under ambient conditions. Control compounds, including a degenerate [2]catenane, were explored in support of the mechanical origin of the switching signature. These SWNT‐based MSTJs operate like previously reported silicon‐based MSTJs, but differently from similar devices incorporating bottom metal electrodes. The relevance of these results with respect to the choice of electrode materials for molecular electronics devices is discussed.     

Influence of defects on the electrical characteristics of mercury-drop junctions: self-assembled monolayers of n-alkanethiolates on rough and smooth silver

This paper compares the structural and electrical characteristics of self-assembled monolayers (SAMs) of n-alkanethiolates, SCn (n = 10, 12, 14), on two types of silver substrates: one used as-deposited (AS-DEP) by an electron-beam evaporator, and one prepared using the method of template-stripping. Atomic force microscopy showed that the template-stripped (TS) silver surfaces were smoother and had larger grains than the AS-DEP surfaces, and reflectance-absorbance infrared spectroscopy showed that SAMs formed on TS substrates were more crystalline than SAMs formed on AS-DEP substrates. The range of current densities, J (A/cm2), measured through mercury-drop junctions incorporating a given SAM on AS-DEP silver was, on average, several orders of magnitude larger than the range of J measured through the same SAM on TS silver, and the AS-DEP junctions failed, on average, 3.5 times more often within five current density-voltage (J-V) scans than did TS junctions (depending on the length of the alkyl chains of the molecules in the SAM). The apparent log-normal distribution of J through the TS junctions suggests that, in these cases, it is the variability in the effective thickness of the insulating layer (the distance the electron travels between electrodes) that results in the uncertainty in J. The parameter describing the decay of current density with the thickness of the insulating layer, beta, was either 0.57 A-1 at V = +0.5 V (calculated using the log-mean of the distribution of values of J) or 0.64 A-1 (calculated using the peak of the distribution of values of J) for the TS junctions; the latter is probably the more accurate. The mechanisms of failure of the junctions, and the degree and sources of uncertainty in current density, are discussed with respect to a variety of defects that occur within Hg-drop junctions incorporating SAMs on silver.     

All-carbon electrode-based fiber-shaped dye-sensitized solar cells

A novel fiber-shaped dye-sensitized solar cell (DSSC) based on an all-carbon electrode is presented, where low-cost, highly-stable, and biocompatible carbon materials are applied to both the photoanode and the counter electrode. The fibrous carbon-based photoanode has a core-shell structure, with carbon fiber core used as conductive substrate to collect carriers and sensitized porous TiO(2) film as shell to harvest light effectively. The highly catalytic all-carbon counter electrode is made from ink carbon coatings and carbon fiber substrate. Results show that the open circuit voltage can be largely improved through engineering at the carbon fiber/TiO(2) interface. An optimized diameter of the photoanode results in an efficiency of 1.9%. It is the first demonstration of efficient DSSCs based on all-carbon electrodes, and the devices are totally free from TCOs or any other expensive electrode materials. Also, this type of solar cell is significant in obtaining bio-friendly all-carbon photovoltaics suitable for large-scale production.     

Molecular electrodes at the exposed edge of metal/insulator/metal trilayer structures

Producing reliable electrical contacts of molecular dimensions has been a critical challenge in the field of molecule-based electronics. Conventional thin film deposition and photolithography techniques have been utilized to construct novel nanometer-sized electrodes on the exposed vertical plane on the edge of a thin film multilayer structure (metal/insulator/metal). Via thiol surface attachment to metal leads, an array of paramagnetic, cyanide-bridged octametal complexes, [(pzTp)FeIII(CN)3]4[NiII(L)]4[O3SCF3]4 (1) [(pzTp) = tetra(pyrazol-1-yl)borate; L = 1-S(acetyl)tris(pyrazolyl)decane], were covalently linked onto the electrodes forming a dominant conduction pathway. A series of molecule-based devices were fabricated using Ni, NiFe, Ta, and Au as metal electrodes separated by insulating Al2O3 spacers, followed by treatment with 1. A series of control experiments were also performed to demonstrate that the conduction path was through tethered metal clusters. The molecular current was analyzed via the Simmons tunnel model, and calculations are consistent with electron tunneling through the alkane ethers to the central metal core. With a Ni/Al2O3/Au molecular electrode, the tether binding was found to be reversible to the top Au layer, allowing for a new class of chemical detection based on the steric bulk of coordinating analytes to disconnect the molecular current path. Simple and economical photolithography/liftoff/self-assembly fabrication techniques afford robust molecular junctions with high reproducibility (>90%) and long operational lifetimes (>1 year).     

Electrochemical electron transfer and its relation to charge transport in single molecule junctions

Ability to control charge transport at nanometer scale lies in the heart of design of fast reliable electronic devices. Molecular electronics thrive to use functional molecules for such transport. If the molecule contains redox center(s), a diode-like or transistor-like behavior can be easily explored by controlling not only the voltage difference between two metallic contacts of the molecular junction but also the potential of one of the contacting electrodes with respect to some reference. Thus, one needs to understand the relationship between electrochemical electron transfer and charge transport in metal–molecule–metal junctions. This review presents latest theoretical approaches toward understanding of such relationship and discusses pivotal experimental works to validate them. Tunneling and hopping pathways may operate in parallel (two-channel model), but experimental conditions dictate the channel preference.     

Influence of the Number of Anchoring Groups on the Electronic and Mechanical Properties of Benzene‐, Anthracene‐ and Pentacene‐Based Molecular Devices

One of the central issues of molecular electronics (ME) is the study of the molecule–metal electrode contacts, and their implications for the conductivity, charge‐transport mechanism, and mechanical stability. In fact, stochastic on/off switching (blinking) reported in STM experiments is a major problem of single‐molecule devices, and challenges the stability and reliability of these systems. Surprisingly, the ambiguous STM results all originate from devices that bind to the metallic electrode through a one‐atom connection. In the present work, DFT is employed to study and compare the properties of a set of simple acenes that bind to metallic electrodes with an increasing number of connections, in order to determine whether the increasing numbers of anchoring groups have a direct repercussion on the stability of these systems. The conductivities of the three polycyclic aromatic hydrocarbons are calculated, as well as their transmission spectra and current profiles. The thermal and mechanical stability of these systems is studied by pulling and pushing the metal–molecule connection. The results show that molecules with more than one connection per electrode exhibit greater electrical efficiency and current stability.     

异型碳纳米管

通过引入缺陷环,直型碳纳米管可连接为不同形态的异型碳纳米管。异型碳纳米管因其在纳米电子科技领域潜在的应用而备受关注。本文综述了异型碳纳米管的合成方法,结构和稳定性的关系,其电学、力学、热学、光学性质以及相关的分子模拟方法在异型碳纳米管研究中的应用进展,并简要介绍了其在电子器件,储氢材料以及其它功能复合材料方面的应用。最后,讨论了目前研究中存在的问题并展望了该领域今后的发展趋势。     

Flexible,Stretchable, and Rechargeable Fiber‐Shaped Zinc–Air Battery Based on Cross‐Stacked Carbon Nanotube Sheets

The fabrication of flexible, stretchable and rechargeable devices with a high energy density is critical for next‐generation electronics. Herein, fiber‐shaped Zn–air batteries, are realized for the first time by designing aligned, cross‐stacked and porous carbon nanotube sheets simultaneously that behave as a gas diffusion layer, a catalyst layer, and a current collector. The combined remarkable electronic and mechanical properties of the aligned carbon nanotube sheets endow good electrochemical properties. They display excellent discharge and charge performances at a high current density of 2 A g⁻¹. They are also flexible and stretchable, which is particularly promising to power portable and wearable electronic devices.     

Flexible,Stretchable, and Rechargeable Fiber‐Shaped Zinc–Air Battery Based on Cross‐Stacked Carbon Nanotube Sheets

The fabrication of flexible, stretchable and rechargeable devices with a high energy density is critical for next‐generation electronics. Herein, fiber‐shaped Zn–air batteries, are realized for the first time by designing aligned, cross‐stacked and porous carbon nanotube sheets simultaneously that behave as a gas diffusion layer, a catalyst layer, and a current collector. The combined remarkable electronic and mechanical properties of the aligned carbon nanotube sheets endow good electrochemical properties. They display excellent discharge and charge performances at a high current density of 2 A g^?1. They are also flexible and stretchable, which is particularly promising to power portable and wearable electronic devices.     

Electron transport and redox reactions in carbon-based molecular electronic junctions

A unique molecular junction design is described, consisting of a molecular mono- or multilayer oriented between a conducting carbon substrate and a metallic top contact. The sp2 hybridized graphitic carbon substrate (pyrolyzed photoresist film, PPF) is flat on the scale of the molecular dimensions, and the molecular layer is bonded to the substrate via diazonium ion reduction to yield a strong, conjugated C-C bond. Molecular junctions were completed by electron-beam deposition of copper, titanium oxide, or aluminium oxide followed by a final conducting layer of gold. Vibrational spectroscopy and XPS of completed junctions showed minimal damage to the molecular layer by metal deposition, although some electron transfer to the molecular layer resulted in partial reduction in some cases. Device yield was high (>80%), and the standard deviations of junction electronic properties such as low voltage resistance were typically in the range of 10-20%. The resistance of PPF/molecule/Cu/Au junctions exhibited a strong dependence on the structure and thickness of the molecular layer, ranging from 0.13 ohms cm2 for a nitrobiphenyl monolayer, to 4.46 ohms cm2 for a biphenyl monolayer, and 160 ohms cm2 for a 4.3 nm thick nitrobiphenyl multilayer. Junctions containing titanium or aluminium oxide had dramatically lower conductance than their PPF/molecule/Cu counterparts, with aluminium oxide junctions exhibiting essentially insulating behavior. However, in situ Raman spectroscopy of PPF/nitroazobenzene/AlO(x)/Au junctions with partially transparent metal contacts revealed that redox reactions occurred under bias, with nitroazobenzene (NAB) reduction occurring when the PPF was biased negative relative to the Au. Similar redox reactions were observed in PPF/NAB/TiO(x)/Au molecular junctions, but they were accompanied by major effects on electronic behavior, such as rectification and persistent conductance switching. Such switching was evident following polarization of PPF/molecule/TiO2/Au junctions by positive or negative potential pulses, and the resulting conductance changes persisted for several minutes at room temperature. The "memory" effect implied by these observations is attributed to a combination of the molecular layer and the TiO2 properties, namely metastable "trapping" of electrons in the TiO2 when the Au is negatively biased.     

烯碳纤维基能源器件的研究进展

纤维状能源器件的研究极大地推动了可穿戴电子设备的快速发展。烯碳纤维主要包括碳纳米管纤维和石墨烯纤维,其微观组成单元具有独特的碳碳共轭分子形态,宏观结构具有高度可调控性,表现出高的比强度、优良的导电性和导热性、以及良好的机械柔韧性等,被广泛应用于先进能源器件的研究和开发,有效促进了柔性可穿戴电子器件的发展。本文综述了烯碳纤维基能源器件包括能量转换和储能器件等的研究和应用进展,具体介绍了烯碳纤维基太阳能电池、湿气发电机、热电发电机、超级电容器以及电化学电池等的最新成果,重点讨论了烯碳纤维基能源器件的制备方法和可穿戴应用,分析了烯碳纤维基储能及能量转换器件面临的问题和挑战,期望能够为未来高性能纤维基可穿戴能源器件的发展提供有价值的研究思路。     

Single-chain and monolayered conjugated polymers for molecular electronics

Exploring the charge transport properties and electronic functions of molecules is of primary interest in the area of molecular electronics. Conjugated polymers (CPs) represent an attractive class of molecular candidates, benefiting from their outstanding optoelectronic properties. However, they have been less studied compared with the small-molecule family, mainly due to the difficulties in incorporating CPs into molecular junctions. In this review, we present a summary on how to fabricate CP-based singlechain and monolayered junctions, then discuss the transport behaviors of CPs in different junction architectures and finally introduce the potential applications of CPs in molecular-scale electronic devices. Although the research on CP-based molecular electronics is still at the initial stage, it is widely accepted that (1) CP chains are able to mediate long-range charge transport if their molecular electronic structures are properly designed, which makes them potential molecular wires, and (2) the intrinsic optoelectronic properties of CPs and the possibility of incorporating desirable functionalities by synthetic strategies imply the potential of employing tailor-made polymeric components as alternatives to small molecules for future molecular-scale electronics.