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Transition From Direct To Inverted Charge Transport Marcus Regions In Molecular Junctions Via Molecular Orbital Gating
L. Yuan, Lejia Wang, A. Garrigues, L. Jiang, H. V. Annadata, Marta Anguera Antonana, E. Barco, C. A. Nijhuis
Published 2018 · Physics, Medicine
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Solid-state molecular tunnel junctions are often assumed to operate in the Landauer regime, which describes essentially activationless coherent tunnelling processes. In solution, on the other hand, charge transfer is described by Marcus theory, which accounts for thermally activated processes. In practice, however, thermally activated transport phenomena are frequently observed also in solid-state molecular junctions but remain poorly understood. Here, we show experimentally the transition from the Marcus to the inverted Marcus region in a solid-state molecular tunnel junction by means of intra-molecular orbital gating that can be tuned via the chemical structure of the molecule and applied bias. In the inverted Marcus region, charge transport is incoherent, yet virtually independent of temperature. Our experimental results fit well to a theoretical model that combines Landauer and Marcus theories and may have implications for the interpretation of temperature-dependent charge transport measurements in molecular junctions.Charge transport in molecular junctions can be incoherent, yet virtually independent of temperature.
This paper references
Reversible Soft Top‐Contacts to Yield Molecular Junctions with Precise and Reproducible Electrical Characteristics
A. Wan (2014)
Molecular electronics with single molecules in solid-state devices.
K. Moth-Poulsen (2009)
Local Gate Control of a Carbon Nanotube Double Quantum Dot
N. Mason (2004)
Large-Area, Ensemble Molecular Electronics: Motivation and Challenges.
A. Vilan (2017)
Kondo effect in a one-electron double quantum dot : Oscillations of the Kondo current in a weak magnetic field
D. Schroer (2006)
Spatial variation of currents and fields due to localized scatterers in metallic conduction
R. Landauer (1988)
Voltage-dependent conductance of a single graphene nanoribbon.
M. Koch (2012)
Redox activity distinguishes solid-state electron transport from solution-based electron transfer in a natural and artificial protein: cytochrome C and hemin-doped human serum albumin.
N. Amdursky (2013)
Field-emission resonances at tip/alpha,omega-mercaptoalkyl ferrocene/Au interfaces studied by STM.
L. Müller-Meskamp (2009)
Structure Matters: Correlating temperature dependent electrical transport through alkyl monolayers with vibrational and photoelectron spectroscopies
H. Shpaisman (2012)
Conformational analysis of diphenylacetylene under the influence of an external electric field.
Y. Li (2007)
Redox‐Induced Asymmetric Electrical Characteristics of Ferrocene‐Alkanethiolate Molecular Devices on Rigid and Flexible Substrates
Hyunhak Jeong (2014)
Gated-Controlled Rectification of a Self-Assembled Monolayer-Based Transistor
E. Mentovich (2013)
Even the Odd Numbers Help: Failure Modes of SAM-Based Tunnel Junctions Probed via Odd-Even Effects Revealed in Synchrotrons and Supercomputers.
D. Thompson (2016)
Molecular orientation of thiol-derivatized tetraphenylporphyrin on gold studied by XPS and NEXAFS
S. Watcharinyanon (2009)
Single-molecule diodes with high rectification ratios through environmental control.
B. Capozzi (2015)
The role of van der Waals forces in the performance of molecular diodes.
Nisachol Nerngchamnong (2013)
The SIESTA method for ab initio order-N materials simulation
J. M. Soler (2001)
Oligo(aryleneethynylene)s with Terminal Pyridyl Groups: Synthesis and Length Dependence of the Tunneling-to-Hopping Transition of Single-Molecule Conductances
X. Zhao (2013)
Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111).
Vijay K. Kanuru (2010)
Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime
S. Y. Sayed (2012)
Charge transport and rectification in arrays of SAM-based tunneling junctions.
C. A. Nijhuis (2010)
On the relationship between molecular state and single electron pictures in simple electrochemical junctions.
A. Migliore (2012)
Temperature dependent charge transport across tunnel junctions of single-molecules and self-assembled monolayers: a comparative study.
A. Garrigues (2016)
Electron transport through double quantum dots
W. G. Wiel (2002)
High-Resolution X-ray Photoelectron Spectra of Organosulfur Monolayers on Au(111): S(2p) Spectral Dependence on Molecular Species
T. Ishida (1999)
A Molecular Diode with a Statistically Robust Rectification Ratio of Three Orders of Magnitude.
L. Yuan (2015)
Eutectic gallium-indium (EGaIn): a moldable liquid metal for electrical characterization of self-assembled monolayers.
R. Chiechi (2008)
Self-assembled monolayers of ferrocene-substituted biphenyl ethynyl thiols on gold.
A. Shaporenko (2006)
Transition from tunneling to hopping in single molecular junctions by measuring length and temperature dependence.
T. Hines (2010)
Electrochemical Methods: Fundamentals and Applications
Allen J. Bard (1980)
Molecular electronics: some views on transport junctions and beyond.
C. Joachim (2005)
On-chip molecular electronic plasmon sources based on self-assembled monolayer tunnel junctions
Wei Du (2016)
Irreversibility and hysteresis in redox molecular conduction junctions.
A. Migliore (2013)
Long-Range Tunneling Processes across Ferritin-Based Junctions.
K. Kumar (2017)
High-Yield Functional Molecular Electronic Devices.
Hyunhak Jeong (2017)
Controlling the direction of rectification in a molecular diode.
L. Yuan (2015)
A Single-Level Tunnel Model to Account for Electrical Transport through Single Molecule- and Self-Assembled Monolayer-based Junctions
A. Garrigues (2016)
R. Metzger (2015)
Electrostatic control over temperature-dependent tunnelling across a single-molecule junction
A. Garrigues (2016)
Single-molecule strong coupling at room temperature in plasmonic nanocavities
R. Chikkaraddy (2016)
Electrical Resistance of Long Conjugated Molecular Wires
Seong Ho Choi (2008)
Progress with molecular electronic junctions: meeting experimental challenges in design and fabrication.
R. McCreery (2009)
Arrays of high quality SAM-based junctions and their application in molecular diode based logic.
A. Wan (2015)
Protocol for disentangling the thermally activated contribution to the tunneling-assisted charge transport. Analytical results and experimental relevance.
I. Bâldea (2017)
Fabrication of nanogapped single-electron transistors for transport studies of individual single-molecule magnets
J. J. Henderson (2007)
Molecular rectification in metal-SAM-metal oxide-metal junctions.
C. A. Nijhuis (2009)
Nonlinear charge transport in redox molecular junctions: a Marcus perspective.
A. Migliore (2011)
Temperature Dependence of Three-Terminal Molecular Junctions with Sulfur End-Functionalized Tercyclohexylidenes
M. Poot (2006)
This paper is referenced by
Charge transport and energy storage at the molecular scale: from nanoelectronics to electrochemical sensing.
Paulo R Bueno (2020)
Electric-field-driven dual-functional molecular switches in tunnel junctions
Yingmei Han (2020)
Charge transport in the inverted Marcus region
Joshua Hihath (2018)
Charge Transfer Through Redox Molecular Junctions in Non-Equilibrated Solvents.
H. Kirchberg (2020)
Design principles of dual-functional molecular switches in solid-state tunnel junctions
D. Thompson (2020)
Understanding Electron Transfer on the Single-Molecule Level
J. O. Thomas (2018)
Introducing mesoscopic charge transfer rates into molecular electronics.
A. Santos (2020)
Tuning Charge Transport in Aromatic-Ring Single-Molecule Junctions via Ionic-Liquid Gating.
N. Xin (2018)
The analysis of charge transport mechanism in molecular junctions based on current-voltage characteristics
Xianneng Song (2020)
Charge and heat current rectification by a double-dot system within the Coulomb blockade regime.
N. A. Zimbovskaya (2020)
Charge-Transport Mechanisms in Azurin-Based Monolayer Junctions
Stephanie Valianti (2019)
Doping hepta-alanine with tryptophan: A theoretical study of its effect on the electrical conductance of peptide-based single-molecule junctions.
W. Schosser (2019)
Marcus Theory of Thermoelectricity in Molecular Junctions
Jakub K Sowa (2019)
Molecular Signature and Activationless Transport in Cobalt‐Terpyridine‐Based Molecular Junctions
Quyen van Nguyen (2020)
Thermoelectric properties of a double-dot system in serial configuration within the Coulomb blockade regime.
N. Zimbovskaya (2020)
Quo vadis, unimolecular electronics?
R. Metzger (2018)
Beyond Marcus theory and the Landauer-Büttiker approach in molecular junctions. II. A self-consistent Born approach.
Jakub K Sowa (2020)
Tuning the charge flow between Marcus regimes in an organic thin-film device
A. Atxabal (2019)
Control of Unipolar/Ambipolar Transport in Single‐Molecule Transistors through Interface Engineering
N. Xin (2020)
Light-Driven Reversible Intermolecular Proton Transfer at Single-Molecule Junctions.
Shuning Cai (2019)
Robust graphene-based molecular devices
Maria El Abbassi (2019)
Understanding resonant charge transport through weakly coupled single-molecule junctions
J. O. Thomas (2019)
Redox Control of Charge Transport in Vertical Ferrocene Molecular Tunnel Junctions
Chuancheng Jia (2020)
A simple vaporous probe with atomic-scale sensitivity to structural ordering and orientation of molecular assembly† †Electronic supplementary information (ESI) available: Additional details for the experiments and data analysis. See DOI: 10.1039/c9sc01656b
Han-Wen Cheng (2019)
Development of Interfacial Nanoassembly Techniques in Functional Nanomaterials
S. Yamamoto (2019)
Orbital Control of Long-Range Transport in Conjugated and Metal-Centered Molecular Electronic Junctions
Ushula M Tefashe (2018)
Transition from stochastic events to deterministic ensemble average in electron transfer reactions revealed by single-molecule conductance measurement
Y. Li (2019)
Beyond Marcus theory and the Landauer-Büttiker approach in molecular junctions: A unified framework.
Jakub K Sowa (2018)
Single-molecule quantum-transport phenomena in break junctions
P. Gehring (2019)
Solid-State Protein Junctions: Cross-Laboratory Study ShowsPreservationof Mechanism at Varying Electronic Coupling
Sabyasachi Mukhopadhyay (2020)