The promise of transition voltage spectroscopy (TVS) is that molecular level positions can be determined in molecular devices without applying extreme voltages. Here, we consider the physics behind TVS in more detail. Remarkably, we find that the Simmons model employed thus far is inconsistent with experimental data. However, a coherent molecular transport model does justify TVS as a spectroscopic tool. Moreover, TVS may become a critical test to distinguish molecular junctions from vacuum tunnel junctions.

This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et(3)N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu(4)NOH) leads to less dense SAMs and the incorporation of Bu(4)N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et(3)N, and Bu(4)NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of β=0.15 Å(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et(3)N was obtained.

We study the interaction between single apex atoms in a metallic contact, using the break junction geometry. By carefully training our samples, we create stable junctions in which no further atomic reorganization takes place. This allows us to study the relation between the so-called jump out of contact (from contact to tunneling regime) and jump to contact (from tunneling to contact regime) in detail. Our data can be fully understood within a relatively simple elastic model, where the elasticity k of the electrodes is the only free parameter. We find 5

Hybrid phototransistors of graphene and the organic semiconductor poly(3-hexylthiophene-2,5-diyl) (P3HT) are presented. Two types of phototransistors are demonstrated with a charge carrier transit time that differs by more than 6 orders of magnitude. High transit time devices are fabricated using a photoresist-free recipe to create large-area graphene transistors made out of graphene grown by chemical vapor deposition. Low transit time devices are fabricated out of mechanically exfoliated graphene on top of mechanically exfoliated hexagonal boron nitride using standard e-beam lithography. Responsivities exceeding 10(5) A/W are obtained for the low transit time devices.

We developed a spin transport model for a diffusive channel with coupled localized states that result in an effective increase of spin precession frequencies and a reduction of spin relaxation times in the system. We apply this model to Hanle spin precession measurements obtained on monolayer epitaxial graphene on SiC(0001). Combined with newly performed measurements on quasi-free-standing monolayer epitaxial graphene on SiC(0001) our analysis shows that the different values for the diffusion coefficient measured in charge and spin transport measurements on monolayer epitaxial graphene on SiC(0001) and the high values for the spin relaxation time can be explained by the influence of localized states arising from the buffer layer at the interface between the graphene and the SiC surface.

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Gold-molecule-gold junctions can be formed by carefully breaking a gold wire in a solution containing dithiolated molecules. Surprisingly, there is little understanding on the mechanical details of the bridge formation process and specifically on the role that the dithiol molecules play themselves. We propose that alkanedithiol molecules have already formed bridges between the gold electrodes before the atomic gold-gold junction is broken. This leads to stabilization of the single atomic gold junction, as observed experimentally. Our data can be understood within a simple spring model.

The electronic properties of large‐area graphene transistors (1 mm × 1 mm) prepared from commercially available graphene on silicon/silicon dioxide modified by self‐assembled bis‐urea‐terthiophene (T3) and bis‐urea‐nonane (C9) molecular wires are reported. Gate spectroscopy on molecularly modified graphene transistors show that the electronic interaction between the molecular wires and the graphene is weak compared to the effect of unwanted dopants.