Evaluation of Carbon Based Molecular Junctions as Practical Photosensors.

Molecular junctions with partially transparent top contacts permit monitoring photocurrents as probes of transport mechanism and potentially could act as photosensors with characteristics determined by the molecular layer inside the device. Previously reported molecular junctions containing nitroazobenzene (NAB) oligomers and oligomers of two different aromatic molecules in bilayers were evaluated for sensitivity, dark signal, responsivity, and limits of detection, in order to determine the device parameters which have the largest effects on photodetection performance. The long-range transport of photogenerated charge carriers permits the use of molecular layers thick enough to absorb a large fraction of the light incident on the layer. Thick layers also reduce the dark current and its associated noise, thus improving the limit of detection to a few nanowatts on a detector area of 0.00125 cm2. Since the photocurrents have much lower activation energy than dark currents do, lowering the detector temperature significantly improves the limit of detection, although the present experiments were limited by environmental and instrumentation noise rather than detector noise. The highest specific detectivity (D*) for the current molecular devices was 3 × 107 cm s1/2 /W (∼109, if only shot noise is considered) at 407 nm in a carbon/NAB/carbon junction with a molecular layer thickness of 28 nm. Although this is in the low end of the 106-1012 range for commonly used photodetectors, improvements in device design based on the current results should increase D* by 3-4 orders of magnitude, while preserving the wavelength selectivity and tunability associated with molecular absorbers. In addition, operation outside the 300-1000 nm range of silicon detectors and very low dark currents may be possible with molecular junctions.

Photostimulated Near-Resonant Charge Transport over 60 nm in Carbon-Based Molecular Junctions.

The bias and temperature dependence of both dark and photoinduced currents in carbon-based molecular junctions were examined over a wide range of oligomeric layer thickness (d) values from 4 to 60 nm. The dark current density versus bias (JV) response of nitroazobenzene molecular junctions exhibits the exponential thickness dependence consistent with coherent tunneling when d < 5 nm, but becomes weakly dependent on d and temperature (T) for d = 15-60 nm. The photocurrent (PC) response is orders of magnitude higher than the dark current for the same d and bias, with very different curve shape and much earlier onset with bias. Although the dark and PC differed greatly in magnitude for d > 14 nm, they both exhibit near zero attenuation coefficients (ß < 0.05 nm-1) and are activationless (Eact < 5 meV) below ∼200 K. For d > 14 nm, both dark and PC become electric field (E) dependent and exhibit approximate overlap of J versus E response for d = 14-60 nm. The value of ln J versus E1/2 is linear for both PC and dark current, with very different magnitudes and slopes. We propose an orbital mediated transport for PC, which involves sequential tunneling of photogenerated electrons and holes between frontier orbitals of adjacent, weakly interacting oligomeric subunits. Such transport is "bulk-limited", E dependent, and nearly activationless due to small tunneling barriers and short distances between adjacent molecular orbitals. In contrast, the dark current is activated and injection limited due to an interfacial energy barrier much larger than that for bulk transport in the junction interior. Rapid, low-barrier transport between orbitals in adjacent molecules should significantly extend the "range" of molecular electronics to >50 nm and avoid the usually strong temperature dependence observed in thicker organic films.

Introducing mesoscopic charge transfer rates into molecular electronics.

It has been demonstrated that mesoscopic rates operate in nanoscale electrochemical systems and, from a fundamental point of view, are able to establish a bridge between electrochemical and molecular electronic concepts. In the present work we offer additional experimental evidence in support of this statement.

Redox Flow Batteries: How to Determine Electrochemical Kinetic Parameters.

Redox flow batteries (RFBs) are promising energy storage candidates for grid deployment of intermittent renewable energy sources such as wind power and solar energy. Various new redox-active materials have been introduced to develop cost-effective and high-power-density next-generation RFBs. Electrochemical kinetics play critical roles in influencing RFB performance, notably the overpotential and cell power density. Thus, determining the kinetic parameters for the employed redox-active species is essential. In this Perspective, we provide the background, guidelines, and limitations for a proposed electrochemical protocol to define the kinetics of redox-active species in RFBs.

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels-Alder Reaction.

The chemical modification of an sp2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution.

Internal Electric Field Modulation in Molecular Electronic Devices by Atmosphere and Mobile Ions.

The internal potential profile and electric field are major factors controlling the electronic behavior of molecular electronic junctions consisting of ∼1-10 nm thick layers of molecules oriented in parallel between conducting contacts. The potential profile is assumed linear in the simplest cases, but can be affected by internal dipoles, charge polarization, and electronic coupling between the contacts and the molecular layer. Electrochemical processes in solutions or the solid state are entirely dependent on modification of the electric field by electrolyte ions, which screen the electrodes and form the ionic double layers that are fundamental to electrode kinetics and widespread applications. The current report investigates the effects of mobile ions on nominally solid-state molecular junctions containing aromatic molecules covalently bonded between flat, conducting carbon surfaces, focusing on changes in device conductance when ions are introduced into an otherwise conventional junction design. Small changes in conductance were observed when a polar molecule, acetonitrile, was present in the junction, and a large decrease of conductance was observed when both acetonitrile (ACN) and lithium ions (Li+) were present. Transient experiments revealed that conductance changes occur on a microsecond-millisecond time scale, and are accompanied by significant alteration of device impedance and temperature dependence. A single molecular junction containing lithium benzoate could be reversibly transformed from symmetric current-voltage behavior to a rectifier by repetitive bias scans. The results are consistent with field-induced reorientation of acetonitrile molecules and Li+ ion motion, which screen the electrodes and modify the internal potential profile and provide a potentially useful means to dynamically alter junction electronic behavior.

Robust Bipolar Light Emission and Charge Transport in Symmetric Molecular Junctions.

Molecular junctions consisting of a Ru(bpy)3 oligomer between conducting carbon contacts exhibit an exponential dependence of junction current on molecular layer thickness (d) similar to that observed for other aromatic devices when d < 4 nm. However, when d > 4 nm, a change in transport mechanism occurs which coincides with light emission in the range of 600-900 nm. Unlike light emission from electrochemical cells or solid-state films containing Ru(bpy)3, emission is bipolar, occurs in vacuum, has rapid rise time (<5 ms), and persists for >10 h. Light emission directly indicates simultaneous hole and electron injection and transport, possibly resonant due to the high electric field present (>3 MV/cm). Transport differs fundamentally from previous tunneling and hopping mechanisms and is a clear "molecular signature" relating molecular structure to electronic behavior.

Modular Flow-Through Platform for Spectroelectrochemical Analysis.

A new type of flow platform for electrochemical and spectroelectrochemical measurements is presented. Finite element method simulations confirm that the hydrodynamic profile within the device is not turbulent and provides an analytical platform for the investigation of homogeneous kinetics, radical lifetimes, and reaction mechanisms. The modular "plug and play" configuration of the platform allows one to carry out electrochemistry and spectroscopy individually or simultaneously. Specific demonstrations of electroanalytical measurements using the flow system platform includes voltammetric analysis of organometallic compounds and quantitative analysis of ascorbic acid in commercial orange juice samples. Combined spectroelectrochemical demonstrations include electrochemical luminescence of ruthenium compounds and ligand exchange reactions of iron complexes using UV-vis spectroscopy.

Robust All-Carbon Molecular Junctions on Flexible or Semi-Transparent Substrates Using "Process-Friendly" Fabrication.

Large area molecular junctions were fabricated on electron-beam deposited carbon (eC) surfaces with molecular layers in the range of 2-5.5 nm between conducting, amorphous carbon contacts. Incorporating eC as an interconnect between Au and the molecular layer improves substrate roughness, prevents electromigration and uses well-known electrochemistry to form a covalent C-C bond to the molecular layer. Au/eC/anthraquinone/eC/Au junctions were fabricated on Si/SiOx with high yield and reproducibility and were unchanged by 10(7) current-voltage cycles and temperatures between 80 and 450 K. Au/eC/AQ/eC/Au devices fabricated on plastic films were unchanged by 10(7) current density vs bias voltage (J-V) cycles and repeated bending of the entire assembled junction. The low sheet resistance of Au/eC substrates permitted junctions with sufficiently transparent electrodes to conduct Raman or UV-vis absorption spectroscopy in either reflection or transmission geometries. Lithographic patterning of Au/eC substrates permitted wafer-scale integration yielding 500 devices on 20 chips on a 100 mm diameter wafer. Collectively, eC on Au provides a platform for fabrication and operation of chemically stable, optically and electrically functional molecules on rigid or flexible materials. The relative ease of processing and the robustness of molecular junctions incorporating eC layers should help address the challenge of economic fabrication of practical, flexible molecular junctions for a potentially wide range of applications.

Cyclometalated Iridium(III) Imidazole Phenanthroline Complexes as Luminescent and Electrochemiluminescent G-Quadruplex DNA Binders.

Six cyclometalated iridium(III) phenanthroimidazole complexes with different modifications to the imidazole phenanthroline ligand exhibit enhanced luminescence when bound to guanine (G-) quadruplex DNA sequences. The complexes bind with low micromolar affinity to human telomeric and c-myc sequences in a 1:1 complex:quadruplex stoichiometry. Due to the luminescence enhancement upon binding to G-quadruplex DNA, the complexes can be used as selective quadruplex indicators. In addition, the electrogenerated chemiluminescence of all complexes increases in the presence of specific G-quadruplex sequences, demonstrating potential for the development of an ECL-based G-quadruplex assay.

Electrogenerated chemiluminescence of iridium-containing ROMP block copolymer and self-assembled micelles.

The electrochemical properties and electrogenerated chemiluminescence (ECL) of an Ir(ppy)2(bpy)(+)-containing ROMP monomer, block copolymer (containing Ir(ppy)2(bpy)(+) complexes, PEG chains, and butyl moieties), and self-assembled micelles were investigated. Following polymerization of the iridium complex, we observed multiple oxidation peaks for the block copolymer in cyclic voltammograms (CV) and differential pulse voltammograms (DPV), suggesting the presence of multiple environments for the iridium complexes along the polymer backbone. The ECL signals from monomer 1 and polymer 2 were reproducible over continuous CV cycles and stable over prolonged potential biases, demonstrating their robustness toward ECL-based detection. Comparison of the ECL signal of the block copolymer, containing multiple iridium complexes attached to the backbone, and the monomeric complex showed enhanced signals for the polymer. In fact, formation and reopening of the self-assembled micelles allowed recovery of the polymer and near complete retention of its original ECL intensity.