Emanuel Lörtscher

Transport Properties of a Single-Molecule Diode

Charge transport through single diblock dipyrimidinyl diphenyl molecules consisting of a donor and acceptor moiety was measured in the low-bias regime and as a function of bias at different temperatures using the mechanically controllable break-junction technique. Conductance histograms acquired at 10 mV reveal two distinct peaks, separated by a factor of 1.5, representing the two orientations of the single molecule with respect to the applied bias. The current-voltage characteristics exhibit a temperature-independent rectification of up to a factor of 10 in the temperature range between 300 and 50 K with single-molecule currents of 45-70 nA at ±1.5 V. The current-voltage characteristics are discussed using a semiempirical model assuming a variable coupling of the molecular energy levels as well as a nonsymmetric voltage drop across the molecular junction, thus shifting the energy levels accordingly. The excellent agreement of the data with the proposed model suggests that the rectification originates from an asymmetric Coulomb blockade in combination with an electric-field-induced level shifting.

Si–InAs heterojunction Esaki tunnel diodes with high current densities

Si–InAs heterojunction p-n diodes were fabricated by growing InAs nanowires in oxide mask openings on silicon substrates. At substrate doping concentrations of 1×1016 and 1×1019 cm−3, conventional diode characteristics were obtained, from which a valence band offset between Si and InAs of 130 meV was extracted. For a substrate doping of 4×1019 cm−3, heterojunction tunnel diode characteristics were obtained showing current densities in the range of 50 kA/cm2 at 0.5 V reverse bias. In addition, in situ doping of the InAs wires was performed using disilane to further boost the tunnel currents up to 100 kA/cm2 at 0.5 V reverse bias for the highest doping ratios.

Wiring molecules into circuits

Inexpensive, functional and atomically precise molecules could be the basis of future electronic devices, but integrating them into circuits will require the development of new ways to control the interface between molecules and electrodes.

Adhesion and friction in mesoscopic graphite contacts

Using friction to guide fabrication Ultralow friction found in certain layered materials such as graphite is important in the construction of nanomechanical devices. Koren et al. combined measurements and modeling to characterize the interaction of sliding graphite planes (see the Perspective by Liechti). This helped them to make small graphite devices that featured rotational pivots and multiple locking positions. Science, this issue p. 679 The measurement and modeling of friction between graphite planes allows for clever engineering of small mechanical devices. [Also see Perspective by Liechti] The weak interlayer binding in two-dimensional layered materials such as graphite gives rise to poorly understood low-friction characteristics. Accurate measurements of the adhesion forces governing the overall mechanical stability have also remained elusive. We report on the direct mechanical measurement of line tension and friction forces acting in sheared mesoscale graphite structures. We show that the friction is fundamentally stochastic in nature and is attributable to the interaction between the incommensurate interface lattices. We also measured an adhesion energy of 0.227 ± 0.005 joules per square meter, in excellent agreement with theoretical models. In addition, bistable all-mechanical memory cell structures and rotational bearings have been realized by exploiting position locking, which is provided solely by the adhesion energy.

Field-induced conductance switching by charge-state alternation in organometallic single-molecule junctions

Charge transport through single molecules can be influenced by the charge and spin states of redox-active metal centres placed in the transport pathway. These intrinsic properties are usually manipulated by varying the molecules electrochemical and magnetic environment, a procedure that requires complex setups with multiple terminals. Here we show that oxidation and reduction of organometallic compounds containing either Fe, Ru or Mo centres can solely be triggered by the electric field applied to a two-terminal molecular junction. Whereas all compounds exhibit bias-dependent hysteresis, the Mo-containing compound additionally shows an abrupt voltage-induced conductance switching, yielding high-to-low current ratios exceeding 1,000 at bias voltages of less than 1.0 V. Density functional theory calculations identify a localized, redox-active molecular orbital that is weakly coupled to the electrodes and closely aligned with the Fermi energy of the leads because of the spin-polarized ground state unique to the Mo centre. This situation provides an additional slow and incoherent hopping channel for transport, triggering a transient charging effect in the entire molecule with a strong hysteresis and large high-to-low current ratios.

Inducing a direct-to-pseudodirect bandgap transition in wurtzite GaAs nanowires with uniaxial stress

Many efficient light-emitting devices and photodetectors are based on semiconductors with, respectively, a direct or indirect bandgap configuration. The less known pseudodirect bandgap configuration can be found in wurtzite (WZ) semiconductors: here electron and hole wave-functions overlap strongly but optical transitions between these states are impaired by symmetry. Switching between bandgap configurations would enable novel photonic applications but large anisotropic strain is normally needed to induce such band structure transitions. Here we show that the luminescence of WZ GaAs nanowires can be switched on and off, by inducing a reversible direct-to-pseudodirect band structure transition, under the influence of a small uniaxial stress. For the first time, we clarify the band structure of WZ GaAs, providing a conclusive picture of the energy and symmetry of the electronic states. We envisage a new generation of devices that can simultaneously serve as efficient light emitters and photodetectors by leveraging the strain degree of freedom.

Charge Transport Through a Cardan-Joint Molecule

The charge transport through a single ruthenium atom clamped by two terpyridine hinges is investigated, both experimentally and theoretically. The metal-bis(terpyridyl) core is equipped with rigid, conjugated linkers of para-acetyl-mercapto phenylacetylene to establish electrical contact in a two-terminal configuration using Au electrodes. The structure of the [Ru(II)(L)(2)](PF(6))(2) molecule is determined using single-crystal X-ray crystallography, which yields good agreement with calculations based on density functional theory (DFT). By means of the mechanically controllable break-junction technique, current-voltage (I-V), characteristics of [Ru(II)(L)(2)](PF(6))(2) are acquired on a single-molecule level under ultra-high vacuum (UHV) conditions at various temperatures. These results are compared to ab initio transport calculations based on DFT. The simulations show that the cardan-joint structural element of the molecule controls the magnitude of the current. Moreover, the fluctuations in the cardan angle leave the positions of steps in the I-V curve largely invariant. As a consequence, the experimental I-V characteristics exhibit lowest-unoccupied-molecular-orbit-based conductance peaks at particular voltages, which are also found to be temperature independent.

Silicon Nanowire Tunnel FETs: Low-Temperature Operation and Influence of High-

In this paper, we demonstrate p-channel tunnel FETs based on silicon nanowires grown with an in situ p-i-n doping profile. The tunnel FETs were fabricated with three different gate dielectrics, SiO₂, Al₂O₃, and HfO₂, and show a performance enhancement when using high-<i>k</i> dielectric materials. The best performance is achieved for the devices using HfO₂ as the gate dielectric, which reach an <i>I</i>_on of 0.1 μA/μm (<i>V</i>_DS = -0.5 V, <i>V</i>_GS = -2 V), combined with an average inverse subthreshold slope (SS) of ~ 120 mV/dec and an <i>I</i>_on/<i>I</i>_off ratio of around 10⁶. For the tunnel FETs with Al₂O₃ as the gate dielectric, different annealing steps were evaluated, and an activation anneal at only 700°C was found to yield the best results. Furthermore, we also investigated the temperature behavior of the tunnel FETs. Ideal tunnel FET behavior was observed for devices having ohmic Ni/Au contacts, and we demonstrate the invariance of both the SS and on-current with temperature, as expected for true tunnel FETs.

k

A series of oligophenylene rods of increasing lengths is synthesized to investigate the charge-transport mechanisms. Methyl groups are attached to the phenyl rings to weaken the electronic overlap of the pi-subsystems along the molecular backbones. Out-of-plane rotation of the phenyl rings is confirmed in the solid state by means of X-ray analysis and in solution by using UV/Vis spectroscopy. The influence of the reduced pi-conjugation on the resonant charge transport is studied at the single-molecule level by using the mechanically controllable break-junction technique. Experiments are performed under ultra-high-vacuum conditions at low temperature (50 K). A linear increase of the conductance gap with increasing number of phenyl rings (from 260 meV for one ring to 580 meV for four rings) is revealed. In addition, the absolute conductance of the first resonant peaks does not depend on the length of the molecular wire. Resonant transport through the first molecular orbital is found to be dominated by charge-carrier injection into the molecule, rather than by the intrinsic resistance of the molecular wire length.

Gate Dielectric

Break-junctions (BJs) enable a pair of atomic-sized electrodes to be created and the relative position between them to be controlled with sub-nanometer accuracy by mechanical means-a level of microscopic control that is not yet achievable by top-down fabrication. Locally, a BJ consists of a single-atom contact, an arrangement that is ideal not only to study various types of quantum point contacts, but also to investigate transport through an individual molecule that can bridge such a junction. In this topical review, we will provide a broad overview on the field of single-molecule electronics, in which BJs serve as the main tool of investigation. To correlate the molecular structure and transport properties to gain a fundamental understanding of the underlying transport mechanisms at the molecular scale, basic experiments that systematically cover all aspects of transport by rational chemical design and tailored experiments are needed. The variety of fascinating transport mechanisms and intrinsic molecular functionalities discovered in the past range from nonlinear transport over conductance switching to quantum interference effects observable even at room temperature. Beside discussing these results, we also look at novel directions and the most recent advances in molecular electronics investigating simultaneously electronic transport and also the mechanical and thermal properties of single-molecule junctions as well as the interaction between molecules and light. Finally, we will describe the requirements for a stepwise transition from fundamental BJ experiments towards technology-relevant architectures for future nanoelectronics applications based on ultimately-scaled molecular building blocks.