Sriharsha V. Aradhya

Single-molecule junctions beyond electronic transport

The idea of using individual molecules as active electronic components provided the impetus to develop a variety of experimental platforms to probe their electronic transport properties. Among these, single-molecule junctions in a metal-molecule-metal motif have contributed significantly to our fundamental understanding of the principles required to realize molecular-scale electronic components from resistive wires to reversible switches. The success of these techniques and the growing interest of other disciplines in single-molecule-level characterization are prompting new approaches to investigate metal-molecule-metal junctions with multiple probes. Going beyond electronic transport characterization, these new studies are highlighting both the fundamental and applied aspects of mechanical, optical and thermoelectric properties at the atomic and molecular scales. Furthermore, experimental demonstrations of quantum interference and manipulation of electronic and nuclear spins in single-molecule circuits are heralding new device concepts with no classical analogues. In this Review, we present the emerging methods being used to interrogate multiple properties in single molecule-based devices, detail how these measurements have advanced our understanding of the structure-function relationships in molecular junctions, and discuss the potential for future research and applications.

Van der Waals interactions at metal/organic interfaces at the single-molecule level

Van der Waals (vdW) interaction, and its subtle interplay with chemically specific interactions and surface roughness at metal/organic interfaces, is critical to the understanding of structure-function relations in diverse areas, including catalysis, molecular electronics and self-assembly. However, vdW interactions remain challenging to characterize directly at the fundamental, single-molecule level both in experiments and in first principles calculations with accurate treatment of the non-local, London dispersion interactions. In particular, for metal/organic interfaces, efforts so far have largely focused on model systems consisting of adsorbed molecules on flat metallic surfaces with minimal specific chemical interaction. Here we show, through measurements of single-molecule mechanics, that pyridine derivatives can bind to nanostructured Au electrodes through an additional binding mechanism beyond the chemically specific N-Au donor-acceptor bond. Using density functional theory simulations we show that vdW interactions between the pyridine ring and Au electrodes can play a key role in the junction mechanics. These measurements thus provide a quantitative characterization of vdW interactions at metal/organic interfaces at the single-molecule level.

Linker Dependent Bond Rupture Force Measurements in Single-Molecule Junctions

We use a modified conducting atomic force microscope to simultaneously probe the conductance of a single-molecule junction and the force required to rupture the junction formed by alkanes terminated with four different chemical link groups which vary in binding strength and mechanism to the gold electrodes. Molecular junctions with amine, methylsulfide, and diphenylphosphine terminated molecules show clear conductance signatures and rupture at a force that is significantly smaller than the measured 1.4 nN force required to rupture the single-atomic gold contact. In contrast, measurements with a thiol terminated alkane which can bind covalently to the gold electrode show conductance and force features unlike those of the other molecules studied. Specifically, the strong Au-S bond can cause structural rearrangements in the electrodes, which are accompanied by substantial conductance changes. Despite the strong Au-S bond and the evidence for disruption of the Au structure, the experiments show that on average these junctions also rupture at a smaller force than that measured for pristine single-atom gold contacts.

Importance of Direct Metal−π Coupling in Electronic Transport Through Conjugated Single-Molecule Junctions

We study the effects of molecular structure on the electronic transport and mechanical stability of single-molecule junctions formed with Au point contacts. Two types of linear conjugated molecular wires are compared: those functionalized with methylsulfide or amine aurophilic groups at (1) both or (2) only one of its phenyl termini. Using scanning tunneling and atomic force microscope break-junction techniques, the conductance of mono- and difunctionalized molecular wires and its dependence on junction elongation and rupture forces were studied. Charge transport through monofunctionalized wires is observed when the molecular bridge is coupled through a S-Au donor-acceptor bond on one end and a relatively weak Au-π interaction on the other end. For monofunctionalized molecular wires, junctions can be mechanically stabilized by installing a second aurophilic group at the meta position that, however, does not in itself contribute to a new conduction pathway. These results reveal the important interplay between electronic coupling through metal-π interactions and quantum mechanical effects introduced by chemical substitution on the conjugated system. This study affords a strategy to deterministically tune the electrical and mechanical properties through molecular wires.

Correlating structure, conductance, and mechanics of silver atomic-scale contacts.

We measure simultaneously force and conductance of Ag metal point-contacts under ambient conditions at room temperature. We observe the formation of contacts with a conductance close to 1 G0, the quantum of conductance, which can be attributed to a single-atom contact, similar to those formed by Au. We also find two additional conductance features at ∼0.4 G0 and ∼1.3 G0, which have been previously ascribed to contacts with oxygen contaminations. Here, using a conductance cross-correlation technique, we distinguish three different atomic-scale structural motifs and analyze their rupture forces and stiffness. Our results allow us to assign the ∼0.4 G0 conductance feature to an Ag-O-Ag contact and the ∼1.3 G0 feature to an Ag-Ag single-atom contact with an oxygen atom in parallel. Utilizing complementary information from force and conductance, we thus demonstrate the correlation of conductance with the structural evolution at the atomic scale.

Nanosecond-Timescale Low Energy Switching of In-Plane Magnetic Tunnel Junctions through Dynamic Oersted-Field-Assisted Spin Hall Effect

We investigate fast-pulse switching of in-plane-magnetized magnetic tunnel junctions (MTJs) within 3-terminal devices in which spin-transfer torque is applied to the MTJ by the giant spin Hall effect. We measure reliable switching, with write error rates down to 10-5, using current pulses as short as just 2 ns in duration. This represents the fastest reliable switching reported to date for any spin-torque-driven magnetic memory geometry and corresponds to a characteristic time scale that is significantly shorter than predicted possible within a macrospin model for in-plane MTJs subject to thermal fluctuations at room temperature. Using micromagnetic simulations, we show that in the three-terminal spin-Hall devices the Oersted magnetic field generated by the pulse current strongly modifies the magnetic dynamics excited by the spin-Hall torque, enabling this unanticipated performance improvement. Our results suggest that in-plane MTJs controlled by Oersted-field-assisted spin-Hall torque are a promising candidate for both cache memory applications requiring high speed and for cryogenic memories requiring low write energies.

Experimental Demonstration of Efficient Spin–Orbit Torque Switching of an MTJ With Sub-100 ns Pulses

Efficient generation of spin currents from charge currents is of high importance for memory and logic applications of spintronics. In particular, generation of spin currents from charge currents in high spin–orbit coupling metals has the potential to provide a scalable solution for embedded memory. We demonstrate a net reduction in the critical charge current for spin torque-driven magnetization reversal via using spin–orbit mediated spin current generation. We scaled the dimensions of the spin–orbit electrode to 400 nm and the nanomagnet to 270 nm

Increased low-temperature damping in yttrium iron garnet thin films

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Electronic transport and mechanical stability of carboxyl linked single-molecule junctions

nm in a three-terminal spin–orbit torque, magnetic tunnel junction (SOT-MTJ) geometry. Our estimated effective spin Hall angle is 0.15–0.20 using the ratio of zero-temperature critical current from spin Hall switching and estimated spin current density for switching the magnet. We show bidirectional transient switching using spin–orbit generated spin torque at 100 ns switching pulses reliably followed by transient read operations. We finally compare the static and dynamic response of the SOT-MTJ with transient spin circuit modeling showing the performance of scaled SOT-MTJs to enable nanosecond class non-volatile MTJs.

Nanosecond magnetization dynamics during spin Hall switching of in-plane magnetic tunnel junctions

We report measurements of the frequency and temperature dependence of ferromagnetic resonance (FMR) for a 15-nm-thick yttrium iron garnet (YIG) film grown by off-axis sputtering. Although the FMR linewidth is narrow at room temperature [corresponding to a damping coefficient