Ferromagnetism in graphene nanoribbons: split versus oxidative unzipped ribbons.

Two types of graphene nanoribbons: (a) potassium-split graphene nanoribbons (GNRs), and (b) oxidative unzipped and chemically converted graphene nanoribbons (CCGNRs) were investigated for their magnetic properties using the combination of static magnetization and electron spin resonance measurements. The two types of ribbons possess remarkably different magnetic properties. While a low-temperature ferromagnet-like feature is observed in both types of ribbons, such room-temperature feature persists only in potassium-split ribbons. The GNRs show negative exchange bias, but the CCGNRs exhibit a "positive exchange bias". Electron spin resonance measurements suggest that the carbon-related defects may be responsible for the observed magnetic behavior in both types of ribbons. Furthermore, information on the proton hyperfine coupling strength has been obtained from hyperfine sublevel correlation experiments performed on the GNRs. Electron spin resonance finds no evidence for the presence of potassium (cluster) related signals, pointing to the intrinsic magnetic nature of the ribbons. Our combined experimental results may indicate the coexistence of ferromagnetic clusters with antiferromagnetic regions leading to disordered magnetic phase. We discuss the possible origin of the observed contrast in the magnetic behaviors of the two types of ribbons studied.

Large intrinsic energy bandgaps in annealed nanotube-derived graphene nanoribbons.

The usefulness of graphene for electronics has been limited because it does not have an energy bandgap. Although graphene nanoribbons have non-zero bandgaps, lithographic fabrication methods introduce defects that decouple the bandgap from electronic properties, compromising performance. Here we report direct measurements of a large intrinsic energy bandgap of approximately 50 meV in nanoribbons (width, approximately 100 nm) fabricated by high-temperature hydrogen-annealing of unzipped carbon nanotubes. The thermal energy required to promote a charge to the conduction band (the activation energy) is measured to be seven times greater than in lithographically defined nanoribbons, and is close to the width of the voltage range over which differential conductance is zero (the transport gap). This similarity suggests that the activation energy is in fact the intrinsic energy bandgap. High-resolution transmission electron and Raman microscopy, in combination with an absence of hopping conductance and stochastic charging effects, suggest a low defect density.

Energy level alignment at organic semiconductor/metal interfaces: effect of polar self-assembled monolayers at the interface.

We determined the shifts in the energy levels of approximately 15 nm thick poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] films deposited on various substrates including self-assembled monolayer (SAM) modified Au surfaces using photoelectron spectroscopy. As the unmodified substrates included Au, indium tin oxide, Si (with native oxide), and Al (with native oxide), a systematic shift in the detected energy levels of the organic semiconductor was observed to follow the work function values of the substrates. Furthermore, we used polar SAMs to alter the work function of the Au substrates. This suggests the opportunity to control the energy level positions of the organic semiconductor with respect to the electrode Fermi level. Photoelectron spectroscopy results showed that, by introducing SAMs on the Au surface, we successfully increased and decreased the effective work function of Au surface. We found that in this case, the change in the effective work function of the metal surface was not reflected as a shift in the energy levels of the organic semiconductor, as opposed to the results achieved with different substrate materials. Our study showed that when a substrate is modified by SAMs (or similarly by any adsorbed molecules), a new effective work function value is achieved; however, it does not necessarily imply that the new modified surface will behave similar to a different metal where the work function is equal to the effective work function of the modified surface. Various models and their possible contribution to this result are discussed.

Fermi level alignment in self-assembled molecular layers: the effect of coupling chemistry.

Photoelectron spectroscopy was used to explore changes in Fermi level alignment, within the pi-pi* gap, arising from modifications to the coupling chemistry of conjugated phenylene ethynylene oligomers to the Au surface. Self-assembled monolayers were formed employing either thiol (4,4'-ethynylphenyl-1-benzenethiol or OPE-T) or isocyanide (4,4'-ethynylphenyl-1-benzeneisocyanide or OPE-NC) coupling. The electronic density of states in the valence region of the two systems are nearly identical with the exception of a shift to higher binding energy by about 0.5 eV for OPE-NC. Corresponding shifts appear in C(1s) spectra and in the threshold near E(F). The lack of change in the optical absorption suggests that a rigid shift of the Fermi level within the pi-pi* gap is the major effect of modifying the coupling chemistry. Qualitative consideration of bonding in each case is used to suggest the influence of chemisorption-induced charge transfer as a potential explanation. Connections to other theoretical and experimental work on the effects of varying coupling chemistries are also discussed.

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.

Controlling charge injection in organic field-effect transistors using self-assembled monolayers.

We have studied charge injection across the metal/organic semiconductor interface in bottom-contact poly(3-hexylthiophene) (P3HT) field-effect transistors, with Au source and drain electrodes modified by self-assembled monolayers (SAMs) prior to active polymer deposition. By using the SAM to engineer the effective Au work function, we markedly affect the charge injection process. We systematically examine the contact resistivity and intrinsic channel mobility and show that chemically increasing the injecting electrode work function significantly improves hole injection relative to untreated Au electrodes.

Kondo resonances and anomalous gate dependence in the electrical conductivity of single-molecule transistors.

We report Kondo resonances in the conduction of single-molecule transistors based on transition metal coordination complexes. We find Kondo temperatures in excess of 50 K, comparable to those in purely metallic systems. The observed gate dependence of the Kondo temperature is inconsistent with observations in semiconductor quantum dots and a simple single-dot-level model. We discuss possible explanations of this effect, in light of electronic structure calculations.

Thermal mismatch strains in sidewall functionalized carbon nanotube/polystyrene nanocomposites.

We present an unusual temperature dependence of thermal strains in 4-(10-hydroxy)decyl benzoate (HDB) modified SWNTPS (SWNT-single wall carbon nanotube, PS-polystyrene) nanocomposites. The strain transfer from the matrix to nanotubes in these nanocomposites, inferred from the frequency change of the Raman active tangential modes of the nanotubes, is enhanced strongly below 300 K, whereas it is vanishingly small at higher temperatures. The increased strain transfer is suggestive of reinforcement of the HDB-SWNTPS nanocomposites at low temperatures. On the other hand, the pristine SWNTs couple weakly to the PS matrix over the entire temperature range of 4.5-410 K. We argue that the strain transfer in HDB-SWNTPS is determined by the thermomechanical properties of the interface region composed of polystyrene plasticized by the tethered alkanelike modifier.

Inelastic electron tunneling via molecular vibrations in single-molecule transistors.

In single-molecule transistors, we observe inelastic cotunneling features that correspond energetically to vibrational excitations of the molecule, as determined by Raman and infrared spectroscopy. This is a form of inelastic electron tunneling spectroscopy of single molecules, with the transistor geometry allowing in situ tuning of the electronic states via a gate electrode. The vibrational features shift and change shape as the electronic levels are tuned near resonance, indicating significant modification of the vibrational states. When the molecule contains an unpaired electron, we also observe vibrational satellite features around the Kondo resonance.

Electrical characterization of metal-molecule-silicon junctions.

Direct assembly of molecules onto silicon surfaces is of particular interest for potential employment in hybrid organic-semiconductor devices. In the study we report here, aryl diazonium salts were used to assemble covalently bound molecular groups on a hydride-passivated, oxide-free n-type Si(111) surface. The reaction of 4-(trimethylsilylethynyl)benzenediazonium tetrafluoroborate generates a molecular layer of 4-(trimethylsilylethynyl)phenylene (TMS-EP) on the n++-Si(111) surface. The monolayer modifies the electrical properties of the interface and exhibits nonlinear current-voltage characteristics, as compared with the ohmic behavior observed from metal-n++-Si(111) junctions. The result of current-voltage measurements at variable temperatures (from 300 to 10 K) on samples made with the TMS-EP molecule does not show significant thermally-activated transport, indicating that tunneling is the dominant transport mechanism. The measured data is compared to a tunneling model.

Molecular wires, switches, and memories.

Design and measurements of molecular wires, switches, and memories offer an increased device capability with reduced elements. We report: Measurements on through-bond electronic transport properties of nanoscale metal-1,4-phenylene diisocyanide-metal junctions are reported, where nonohmic thermionic emission is the dominant process, with isocyanide-Pd showing the lowest thermionic barrier of 0.22 eV; robust and large reversible switching behavior in an electronic device that utilizes molecules containing redox centers as the active component, exhibiting negative differential resistance (NDR) and large on-off peak-to-valley ratio (PVR) are realized; erasable storage of higher conductivity states in these redox-center-containing molecular devices are observed; and a two-terminal electronically programmable and erasable molecular memory cell with long bit retention time is demonstrated.

Functionalization of carbon nanotubes by electrochemical reduction of aryl diazonium salts: a bucky paper electrode.

Small-diameter (ca. 0.7 nm) single-wall carbon nanotubes are predicted to display enhanced reactivity relative to larger-diameter nanotubes due to increased curvature strain. The derivatization of these small-diameter nanotubes via electrochemical reduction of a variety of aryl diazonium salts is described. The estimated degree of functionalization is as high as one out of every 20 carbons in the nanotubes bearing a functionalized moiety. The functionalizing moieties can be removed by heating in an argon atmosphere. Nanotubes derivatized with a 4-tert-butylbenzene moiety were found to possess significantly improved solubility in organic solvents. Functionalization of the nanotubes with a molecular system that has exhibited switching and memory behavior is shown. This represents the marriage of wire-like nanotubes with molecular electronic devices.

Conductance switching in single molecules through conformational changes.

We tracked over time the conductance switching of single and bundled phenylene ethynylene oligomers isolated in matrices of alkanethiolate monolayers. The persistence times for isolated and bundled molecules in either the ON or OFF switch state range from seconds to tens of hours. When the surrounding matrix is well ordered, the rate at which the inserted molecules switch is low. Conversely, when the surrounding matrix is poorly ordered, the inserted molecules switch more often. We conclude that the switching is a result of conformational changes in the molecules or bundles, rather than electrostatic effects of charge transfer.

Benzyltriethylammonium dichloroiodate/sodium bicarbonate combination as an inexpensive, environmentally friendly, and mild iodinating reagent for anilines.

[reaction: see text]. Monoiodinated anilines were prepared in good to excellent yields by the action of benzyltriethylammonium dichloroiodate on anilines in the presence of sodium bicarbonate and methanol. The iodinating reagent was prepared in an environmentally friendly fashion without the use of organic solvents.

Phenylene ethynylene diazonium salts as potential self-assembling molecular devices.

[reaction: see text]. Functionalized diazonium salts for molecular electronic devices are prepared by the reaction of the corresponding anilines with NOBF4 in sulfolane-acetonitrile solvent.

Synthesis and preliminary testing of molecular wires and devices.

Presented here are several convergent synthetic routes to conjugated oligo(phenylene ethynylene)s. Some of these oligomers are free of functional groups, while others possess donor groups, acceptor groups, porphyrin interiors, and other heterocyclic interiors for various potential transmission and digital device applications. The syntheses of oligo(phenylene ethynylene)s with a variety of end groups for attachment to numerous metal probes and surfaces are presented. Some of the functionalized molecular systems showed linear, wire-like, current versus voltage (I(V)) responses, while others exhibited nonlinear I(V) curves for negative differential resistance (NDR) and molecular random access memory effects. Finally, the syntheses of functionalized oligomers are described that can form self-assembled monolayers on metallic electrodes that reduce the Schottky barriers. Information from the Schottky barrier studies can provide useful insight into molecular alligator clip optimizations for molecular electronics.

Molecular electronics. Synthesis and testing of components.

Molecular electronics involves the use of single or small packets of molecules as the fundamental units for computing. While initial targets are the substitution of solid-state wires and devices with molecules, long-range goals involve the development of novel addressable electronic properties from molecules. A comparison of traditional solid-state devices to molecular systems is described. Issues of cost and ease of manufacture are outlined, along with the syntheses and testing of molecular wires and devices.