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 (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 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.
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.
Abstract: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 3-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-planeMTJs 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. Keywords:spintronics, spin Hall effect, magnetic tunnel junction, magnetic memory, spin orbit torque,Magnetic random access memory (MRAM) controlled using spin transfer torque (STT) 1-3 , using either in-plane [4][5][6] or perpendicularly magnetized 7,8 magnetic tunnel junctions (MTJs), holds promise for replacing existing best-in-class memory technologies in several application domains because it offers the potential for non-volatility, unlimited read and write endurance, low write energy, and low standby power. For the wide application of STT-MRAM technology it is also crucial to achieve high-speed switching with low write error rates (WERs). Currently, the fastest reliable (< 10 -5 WER) switching times reported for conventional 2-terminal STT-MRAM are 35 ns for in-plane MTJs, 6 and 4 ns for perpendicular MTJs. 8 Theoretical and experimental analyses have led to skepticism about the possibility for significant improvements in switching speed and reliability, particularly for in-plane magnetized devices. 4,9 Consequently, the search for speed has led to more ambitious proposals including orthogonal spin-transfer (OST) MRAM, 10 where sub-ns switching has been demonstrated, but via a precessional non-deterministic mechanism that thus far has not allowed for competitive WERs. Here we investigate the speed and reliability of spin-orbit torque 11-15 switching in three-terminal devices [16][17][18][19][20] that utilize the spin Hall effect (SHE) 21,22 to achieve efficient switching of an in-plane magnetized MTJ. We demonstrate reliable (≤10 -5 WER) switching using current pulses only 2 ns long. This is faster than the best reported value for reliable switching of any previous spin-torque MRAM device 4-9 -in-plane or perpendicular -with a characteristic time scale even faster than the theoretical limit expected for in-plane-magnetized MTJs in the macrospin approximation.9,23,24 Figure 1a sh...
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.
Future applications of spin-orbit torque will require new mechanisms to improve the efficiency for switching nanoscale magnetic tunnel junctions (MTJs), while also controlling the magnetic dynamics to achieve fast, nanosecond scale performance with low write error rates. Here we demonstrate a strategy to simultaneously enhance the interfacial magnetic anisotropy energy and suppress interfacial spin memory loss by introducing sub-atomic and monatomic layers of Hf at the top and bottom interfaces of the ferromagnetic free layer of an in-plane magnetized three-terminal MTJ device. When combined with a beta-W spin Hall channel that generates spin-orbit torque, the cumulative effect is a switching current density of 5.4 x 10 6 A/cm 2 , more than a factor of 3 lower than demonstrated in any other spin-orbit-torque magnetic memory device at room temperature, and highly reliable switching with current pulses only 2 ns long. *buhrman@cornell.edu.
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.
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