Controlling destructive quantum interference in tunneling junctions comprising self-assembled monolayers via bond topology and functional groups

Zhang, Yanxi; Ye, Gang; Soni, Saurabh; Qiu, Xinkai; Krijger, Theodorus L.; Jonkman, Harry T.; Carlotti, Marco; Sauter, Eric; Zharnikov, Michael; Chiechi, Ryan C.

doi:10.1039/c8sc00165k

Cited by 53 publications

(87 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Similar conclusions have been drawn also in somewhat more recent experiments on coupled benzene rings [19]. More recent experimental efforts have even established such subtle correlations like the effects bond topology and electronegativity of atomic sites can have on the degree and the location of QI features in molecular wires [20]. It is suggested that combination of stimuli-response and QI can be an efficient strategy to enhance isomer recognition and conductance switching in single-molecule junctions [21].…”

Section: Introductionsupporting

confidence: 72%

Quantum Interference in Real-Time Electron-Dynamics: Gaining Insights from Time-Dependent Configuration Interaction Simulations

Ramakrishnan¹

2019

Preprint

View full text Add to dashboard Cite

Femtosecond electron dynamics based on time-dependent configuration interaction (TDCI) is a numerically rigorous approach for quantitative modeling of electron-injection across molecular junctions. Our simulations of cyanobenzene thiolates---para- and meta-linked to an acceptor gold atom---corroborate aromatic resonance stabilization effects and show donor states \emph{conjugating} with the benzene $\pi$-network to exhibit superior electron-injection dynamics across the para-linked isomer compared to the meta counterpart. For a \emph{non-conjugating} initial state, we find electron-injection through the meta-channel to stem from non-resonant quantum mechanical tunneling. Furthermore, we demonstrate quantum interference to drive para- vs. meta- selectivity in the coherent evolution of superposed $\pi$(CN)- and $\sigma$(NC-C)-type wavepackets. Analyses reveal that in the para-linked molecule, $\sigma$, and $\pi$ MOs localized at the donor terminal are \emph{in-phase} leading to constructive interference of electron density distribution while phase-flip of one of the MOs in the meta-linked molecule results in destructive interference. The findings reported here suggest that \emph{a priori} detection of orbital phase-flip and quantum coherence conditions can aid in molecular device design strategies.

show abstract

Section: Introductionsupporting

confidence: 72%

Quantum Interference in Real-Time Electron-Dynamics: Gaining Insights from Time-Dependent Configuration Interaction Simulations

Ramakrishnan¹

2019

Preprint

View full text Add to dashboard Cite

show abstract

“…[9] Constructive QI (CQI) occurs when the interference pattern has al arge amplitude at the point of molecular contact to both the source and drain electrodes,causing high through-molecule conductance.C onversely,d estructive QI (DQI) results in alow amplitude of the propagating electron wave at one or both of the electrode-molecule contacts, causing extremely low through-molecule conductance. [10] The ability to convert between these two scenarios by tuning the molecular pathways can offer an exciting range of opportunities to regulate charge transport through molecules,without changing the molecular backbone structure,l ength, or redox state.…”

Section: Introductionmentioning

confidence: 99%

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single‐Molecule Conductance

et al. 2019

View full text Add to dashboard Cite

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions.

show abstract

“…[1][2][3][4] Single-molecule electronic junctions have been investigated intensively over the past decade, not only as stepping stones toward functional devices and circuits made from collections of molecules but also because their room-temperature electrical conductance is controlled by quantum interference (QI). [5][6][7][8][9][10][11][12][13][14][15] Figure 1A illustrates an example of a non-classical QI effect, in a graphene-like (anthanthrene) molecular core, when an electrical current is injected and collected via the green arrows, or alternatively, via the red arrows. If the core behaved like a classical resistor network, then the electrical conductance for these two connectivities would be approximately equal.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembled Molecular-Electronic Films Controlled by Room Temperature Quantum Interference

Famili

Jia

Liu

et al. 2019

Chem

View full text Add to dashboard Cite

Molecular-scale electronics is a branch of nanotechnology, which utilizes molecules as electronic components. Here, we demonstrate that roomtemperature quantum interference (QI) effects identified in single molecules can be translated into ultra-thin-film materials. This breakthrough opens up avenues for exploiting QI in the design of new materials with enhanced electrical, thermal, and sensing functionality. Field effect control using an ionic liquid gate demonstrates that QI can be used to optimize the on-off ratio of ultra-thin-film transistors. (X.D.) HIGHLIGHTS A vertical tunneling organic transistor on grapheneRoom-temperature intramolecular quantum interference in self-assembled monolayers Field effect tuning of the energy levels of a self-assembled monolayer on graphene Quantum interference optimizes the on-off ratio of ultra-thin-film transistors Famili et al., Chem 5,[474][475][476][477][478][479][480][481][482][483][484] February 14, SUMMARYIf single-molecule, room-temperature, quantum interference (QI) effects could be translated into massively parallel arrays of molecules located between planar electrodes, QI-controlled molecular transistors would become available as building blocks for future electronic devices. Here, we demonstrate unequivocal signatures of room-temperature QI in vertical tunneling transistors, formed from self-assembled monolayers (SAMs), with stable room-temperature switching operations. As a result of constructive QI effects, the conductances of the junctions formed from anthanthrene-based molecules with two different connectivities differ by a factor of 34, which can further increase to 173 by controlling the molecule-electrode interface with different terminal groups. Field-effect control is achieved using an ionic liquid gate, whose strong vertical electric field penetrates through the graphene layer and tunes the energy levels of the SAMs. The resulting room-temperature on-off current ratio of the lowestconductance SAMs can reach up to 306, about one order of magnitude higher than that of the highest-conductance SAMs.

show abstract

Controlling destructive quantum interference in tunneling junctions comprising self-assembled monolayers via bond topology and functional groups

Abstract: Three different benzodithiophene derivatives were designed to isolate the effects of bond topology from that of functional groups in quantum interference to examine the role of the quinone functionality separate from cross-conjugation.

Cited by 53 publications

References 71 publications

Quantum Interference in Real-Time Electron-Dynamics: Gaining Insights from Time-Dependent Configuration Interaction Simulations

Quantum Interference in Real-Time Electron-Dynamics: Gaining Insights from Time-Dependent Configuration Interaction Simulations

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single‐Molecule Conductance

Self-Assembled Molecular-Electronic Films Controlled by Room Temperature Quantum Interference

Contact Info

Product

Resources

About