On the Mechanical and Electronic Properties of Thiolated Gold Nanocrystals

We present a quantitative exploration, combining experiment and simulation, of the mechanical and electronic properties, as well as the modifications induced by an alkylthiolated coating, at the single NP level. We determine the response of the NPs to external pressure in a controlled manner by using an atomic force microscope tip. We find a strong reduction of their Young modulus, as compared to bulk gold, and a significant influence of strain in the electronic properties of the alkylthiolated NPs. Electron transport measurements of tiny molecular junctions (NP/alkylthiol/CAFM tip) show that the effective tunnelling barrier through the adsorbed monolayer strongly decreases with increasing the applied load, which translates in a remarkable and unprecedented increase of the tunnel current. These observations are successfully explained using simulations based on finite element analysis (FEA) and first-principles calculations that permit to consider the coupling between the mechanical response of the system and the electric dipole variations at the interface.

Water Electrolysis and Energy Harvesting with 0D Ion-Sensitive Field-Effect Transistors

The relationship of the gas bubble size to the size distribution critically influences the effectiveness of electrochemical processes. Several optical and acoustical techniques have been used to characterize the size and emission frequency of bubbles. Here, we used zero-dimensional (0D) ion-sensitive field-effect transistors (ISFETs) buried under a microbath to detect the emission of individual bubbles electrically and to generate statistics on the bubble emission time. The bubble size was evaluated via a simple model of the electrolytic current. We suggest that energy lost during water electrolysis could be used to generate electric pulses at an optimal efficiency with an array of 0D ISFETs.

A Crown-Ether Loop-Derivatized Oligothiophene Doubly Attached on Gold Surface as Cation-Binding Switchable Molecular Junction

A crown-ether dithiol quaterthiophene is synthesized for its covalent immobilization by double fixation on gold surface. While the corresponding dithioester precursor exhibits Pb2+ complexation properties in solution as evidenced by UV-vis spectroscopy and cyclic voltammetry, this Pb2+ affinity is still maintained for monolayers of the dithiol on gold. In addition, current-voltage measurements by Eutectic GaIn drop contact on the monolayer show a significant increase (up to 1.6 x 1E3) of the current at low bias after Pb2+ complexation.

Low Frequency Dielectric Loss of Metal/Insulator/Organic Semiconductor Junctions in Ambient Conditions

The complex admittance of metal/oxide/pentacene thin film junctions is investigated under ambient conditions. At low frequencies, a contribution attributed to proton diffusion through the oxide is seen. This diffusion is shown to be anomalous and is believed to be also at the origin of the bias stress effect observed in organic field effect transistors. At higher frequencies, two dipolar contributions are evidenced, attributed to defects located one at the organic/oxide interface or within the organic, and the other in the bulk of the oxide. These two dipolar responses show different dynamic properties that manifest themselves in the admittance in the form of a Debye contribution for the defects located in the oxide, and of a Cole-Cole contribution for the defects related to the organic.

A Silicon Nanowire Ion-Sensitive Field-Effect-Transistor with elementary charge sensitivity

We investigate the mechanisms responsible for the low-frequency noise in liquid-gated nano-scale silicon nanowire field-effect transistors (SiNW-FETs) and show that the charge-noise level is lower than elementary charge. Our measurements also show that ionic strength of the surrounding electrolyte has a minimal effect on the overall noise. Dielectric polarization noise seems to be at the origin of the 1/f noise in our devices. The estimated spectral density of charge noise Sq = 1.6x10-2 e/sqr(Hz) at 10 Hz opens the door to metrological studies with these SiNW-FETs for the electrical detection of a small number of molecules.

High on-off conductance switching ratio in optically-driven self-assembled conjugated molecular systems

A new azobenzene-thiophene molecular switch is designed, synthesized and used to form self-assembled monolayers (SAM) on gold. An on/off conductance ratio up to 7x1E3 (with an average value of 1.5x1E3) is reported. The on conductance state is clearly identified to the cis isomer of the azobenzene moiety. The high on/off ratio is explained in terms of photo-induced, configuration-related, changes in the electrode-molecule interface energetics (changes in the energy position of the molecular orbitals with respect to the Fermi energy of electrodes) in addition to changes in the tunnel barrier length (length of the molecules). First principles DFT calculations demonstrate a better delocalization of the frontier orbitals, as well as a stronger electronic coupling between the azobenzene moiety and the electrode for the cis configuration over the trans one. Measured photoionization cross-sections for the molecules in the SAM are close to the known values for azobenzene derivatives in solution.

Gold nanoparticle-pentacene memory-transistors

We demonstrate an organic memory-transistor device based on a pentacene-gold nanoparticles active layer. Gold (Au) nanoparticles are immobilized on the gate dielectric (silicon dioxide) of a pentacene transistor by an amino-terminated self-assembled monolayer. Under the application of writing and erasing pulses on the gate, large threshold voltage shift (22 V) and on/off drain current ratio of ~3E4 are obtained. The hole field-effect mobility of the transistor is similar in the on and off states (less than a factor 2). Charge retention times up to 4500 s are observed. The memory effect is mainly attributed to the Au nanoparticles.