Michel Calame

Light-Controlled Conductance Switching of Ordered Metal-Molecule-Metal Devices

We demonstrate reversible, light-controlled conductance switching of molecular devices based on photochromic diarylethene molecules. These devices consist of ordered, two-dimensional lattices of gold nanoparticles, in which neighboring particles are bridged by switchable molecules. We independently confirm that reversible isomerization of the diarylethenes employed is at the heart of the room-temperature conductance switching. For this, we take full advantage of the possibility to use optical spectroscopy to follow molecular switching in these samples.

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.

Nernst Limit in Dual-Gated Si-Nanowire FET Sensors

Field effect transistors (FETs) are widely used for the label-free detection of analytes in chemical and biological experiments. Here we demonstrate that the apparent sensitivity of a dual-gated silicon nanowire FET to pH can go beyond the Nernst limit of 60 mV/pH at room temperature. This result can be explained by a simple capacitance model including all gates. The consistent and reproducible results build to a great extent on the hysteresis- and leakage-free operation. The dual-gate approach can be used to enhance small signals that are typical for bio- and chemical sensing at the nanoscale.

Electrical conductance of conjugated oligomers at the single molecule level.

We determine and compare, at the single molecule level and under identical environmental conditions, the electrical conductance of four conjugated phenylene oligomers comprising terminal sulfur anchor groups with simple structural and conjugation variations. The comparison shows that the conductance of oligo(phenylene vinylene) (OPV) is slightly higher than that of oligo(phenylene ethynylene) (OPE). We find that solubilizing side groups do neither prevent the molecules from being anchored within a break junction nor noticeably influence the conductance value.

Graphene transistors are insensitive to pH changes in solution.

We observe very small gate-voltage shifts in the transfer characteristic of as-prepared graphene field-effect transistors (GFETs) when the pH of the buffer is changed. This observation is in strong contrast to Si-based ion-sensitive FETs. The low gate-shift of a GFET can be further reduced if the graphene surface is covered with a hydrophobic fluorobenzene layer. If a thin Al-oxide layer is applied instead, the opposite happens. This suggests that clean graphene does not sense the chemical potential of protons. A GFET can therefore be used as a reference electrode in an aqueous electrolyte. Our finding sheds light on the large variety of pH-induced gate shifts that have been published for GFETs in the recent literature.

Cyclic Conductance Switching in Networks of Redox-Active Molecular Junctions

Redox-active dithiolated tetrathiafulvalene derivatives (TTFdT) were inserted in two-dimensional nanoparticle arrays to build interlinked networks of molecular junctions. Upon oxidation of the TTFdT to the dication state, we observed a conductance increase of the networks by up to 1 order of magnitude. Successive oxidation and reduction cycles demonstrated a clear switching behavior of the molecular junction conductance. These results show the potential of interlinked nanoparticle arrays as chemical sensors.

Feedback controlled electromigration in four-terminal nanojunctions

The authors have developed a fast, yet highly reproducible method to fabricate metallic electrodes with nanometer separation using electromigration (EM). They employ four terminal instead of two-terminal devices in combination with an analog feedback to maintain the voltage U over the junction constant. After the initialization phase (U≲0.2V), during which the temperature T increases by 80–150°C, EM sets in shrinking the wire locally. This quickly leads to a transition from the diffusive to a quasiballistic regime (0.2V≲U≲0.6V). At the end of this second regime, a gap forms (U≳0.6V). Remarkably, controlled electromigration is still possible in the quasiballistic regime.

Understanding the Electrolyte Background for Biochemical Sensing with Ion-Sensitive Field-Effect Transistors

Silicon nanowire field-effect transistors have attracted substantial interest for various biochemical sensing applications, yet there remains uncertainty concerning their response to changes in the supporting electrolyte concentration. In this study, we use silicon nanowires coated with highly pH-sensitive hafnium oxide (HfO(2)) and aluminum oxide (Al(2)O(3)) to determine their response to variations in KCl concentration at several constant pH values. We observe a nonlinear sensor response as a function of ionic strength, which is independent of the pH value. Our results suggest that the signal is caused by the adsorption of anions (Cl(-)) rather than cations (K(+)) on both oxide surfaces. By comparing the data to three well-established models, we have found that none of those can explain the present data set. Finally, we propose a new model which gives excellent quantitative agreement with the data.

Surface plasmon enhanced photoconductance of gold nanoparticle arrays with incorporated alkane linkers

We report on a photoconductive gain effect in two-dimensional arrays of gold nanoparticles (NPs) in which alkane molecules are inserted. The NP arrays are formed by a self-assembly process from alkanethiol-coated gold NPs, and subsequently they are patterned on a Si/SiO2 chip by a microcontact printing technique. We find that the photoconductance of the arrays is strongly enhanced at the frequency of the surface plasmon of the NPs. We interpret the observation as a bolometric enhancement in the conductance of the NP arrays upon excitation of the surface plasmon resonance.

Regulating a Benzodifuran Single Molecule Redox Switch via Electrochemical Gating and Optimization of Molecule/Electrode Coupling

We report a novel strategy for the regulation of charge transport through single molecule junctions via the combination of external stimuli of electrode potential, internal modulation of molecular structures, and optimization of anchoring groups. We have designed redox-active benzodifuran (BDF) compounds as functional electronic units to fabricate metal-molecule-metal (m-M-m) junction devices by scanning tunneling microscopy (STM) and mechanically controllable break junctions (MCBJ). The conductance of thiol-terminated BDF can be tuned by changing the electrode potentials showing clearly an off/on/off single molecule redox switching effect. To optimize the response, a BDF molecule tailored with carbodithioate (-CS2(-)) anchoring groups was synthesized. Our studies show that replacement of thiol by carbodithioate not only enhances the junction conductance but also substantially improves the switching effect by enhancing the on/off ratio from 2.5 to 8.