Cryogenic Memory Architecture Integrating Spin Hall Effect based Magnetic Memory and Superconductive Cryotron Devices.

One of the most challenging obstacles to realizing exascale computing is minimizing the energy consumption of L2 cache, main memory, and interconnects to that memory. For promising cryogenic computing schemes utilizing Josephson junction superconducting logic, this obstacle is exacerbated by the cryogenic system requirements that expose the technology's lack of high-density, high-speed and power-efficient memory. Here we demonstrate an array of cryogenic memory cells consisting of a non-volatile three-terminal magnetic tunnel junction element driven by the spin Hall effect, combined with a superconducting heater-cryotron bit-select element. The write energy of these memory elements is roughly 8 pJ with a bit-select element, designed to achieve a minimum overhead power consumption of about 30%. Individual magnetic memory cells measured at 4 K show reliable switching with write error rates below 10-6, and a 4 × 4 array can be fully addressed with bit select error rates of 10-6. This demonstration is a first step towards a full cryogenic memory architecture targeting energy and performance specifications appropriate for applications in superconducting high performance and quantum computing control systems, which require significant memory resources operating at 4 K.

Quantitative bond energetics in atomic-scale junctions.

A direct measurement of the potential energy surface that characterizes individual chemical bonds in complex materials has fundamental significance for many disciplines. Here, we demonstrate that the energy profile for metallic single-atom contacts and single-molecule junctions can be mapped by fitting ambient atomic force microscope measurements carried out in the near-equilibrium regime to a physical, but simple, functional form. We extract bond energies for junctions formed through metallic bonds as well as metal-molecule link bonds from atomic force microscope data and find that our results are in excellent quantitative agreement with density functional theory based calculations for exemplary junction structures. Furthermore, measurements from a large number of junctions can be collapsed to a single, universal force-extension curve, thus revealing a surprising degree of similarity in the overall shape of the potential surface that governs these chemical bonds. Compared to previous studies under ambient conditions where analysis was confined to trends in rupture force, our approach significantly expands the quantitative information extracted from these measurements, particularly allowing analysis of the trends in bond energy directly.

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.

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.

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.

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.

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

We characterize electron transport across Au-molecule-Au junctions of heterogeneous carboxyl and methyl sulfide terminated saturated and conjugated molecules. Low-bias conductance measurements are performed using the scanning tunneling microscopy based break-junction technique in the presence of solvents and at room temperature. For a series of alkanes with 1-4 carbon atoms in the hydrocarbon chain, our results show an exponential decrease in conductance with increasing molecule length characterized by a decay constant of 0.9 ± 0.1 per methylene group. Control measurements in pH 11 solutions and with COOMe terminations suggest that the carboxylic acid group binds through the formation of a COO(-)-Au bond. Simultaneous measurements of conductance and force across these junctions yield a rupture force of 0.6 ± 0.1 nN, comparable to that required to rupture a Au-SMe bond. By establishing reliable, in situ junction formation, these experiments provide a new approach to probe electronic properties of carboxyl groups at the single molecule level.

Dissecting contact mechanics from quantum interference in single-molecule junctions of stilbene derivatives.

Electronic factors in molecules such as quantum interference and cross-conjugation can lead to dramatic modulation and suppression of conductance in single-molecule junctions. Probing such effects at the single-molecule level requires simultaneous measurements of independent junction properties, as conductance alone cannot provide conclusive evidence of junction formation for molecules with low conductivity. Here, we compare the mechanics of the conducting para-terminated 4,4'-di(methylthio)stilbene and moderately conducting 1,2-bis(4-(methylthio)phenyl)ethane to that of insulating meta-terminated 3,3'-di(methylthio)stilbene single-molecule junctions. We simultaneously measure force and conductance across single-molecule junctions and use force signatures to obtain independent evidence of junction formation and rupture in the meta-linked cross-conjugated molecule even when no clear low-bias conductance is measured. By separately quantifying conductance and mechanics, we identify the formation of atypical 3,3'-di(methylthio)stilbene molecular junctions that are mechanically stable but electronically decoupled. While theoretical studies have envisaged many plausible systems where quantum interference might be observed, our experiments provide the first direct quantitative study of the interplay between contact mechanics and the distinctively quantum mechanical nature of electronic transport in single-molecule junctions.

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.

Mechanics and chemistry: single molecule bond rupture forces correlate with molecular backbone structure.

We simultaneously measure conductance and force across nanoscale junctions. A new, two-dimensional histogram technique is introduced to statistically extract bond rupture forces from a large data set of individual junction elongation traces. For the case of Au point contacts, we find a rupture force of 1.4 ± 0.2 nN, which is in good agreement with previous measurements. We then study systematic trends for single gold metal-molecule-metal junctions for a series of molecules terminated with amine and pyridine linkers. For all molecules studied, single molecule junctions rupture at the Au-N bond. Selective binding of the linker group allows us to correlate the N-Au bond-rupture force to the molecular backbone. We find that the rupture force ranges from 0.8 nN for 4,4' bipyridine to 0.5 nN in 1,4 diaminobenzene. These experimental results are in excellent quantitative agreement with density functional theory based adiabatic molecular junction elongation and rupture calculations.