← Back to Search
Length-dependent Thermopower Of Highly Conducting Au-C Bonded Single Molecule Junctions.
J. R. Widawsky, W. Chen, H. Vázquez, T. Kim, R. Breslow, M. Hybertsen, L. Venkataraman
Published 2013 · Materials Science, Medicine
Download PDFAnalyze on Scholarcy
We report the simultaneous measurement of conductance and thermopower of highly conducting single-molecule junctions using a scanning tunneling microscope-based break-junction setup. We start with molecular backbones (alkanes and oligophenyls) terminated with trimethyltin end groups that cleave off in situ to create junctions where terminal carbons are covalently bonded to the Au electrodes. We apply a thermal gradient across these junctions and measure their conductance and thermopower. Because of the electronic properties of the highly conducting Au-C links, the thermoelectric properties and power factor are very high. Our results show that the molecular thermopower increases nonlinearly with the molecular length while conductance decreases exponentially with increasing molecular length. Density functional theory calculations show that a gateway state representing the Au-C covalent bond plays a key role in the conductance. With this as input, we analyze a series of simplified models and show that a tight-binding model that explicitly includes the gateway states and the molecular backbone states accurately captures the experimentally measured conductance and thermopower trends.
This paper references
End-Group Induced Charge Transfer in Molecular Junctions: Effect on Electronic-Structure and Thermopower
Janakiraman Balachandran (2012)
Complex band structure, decay lengths, and Fermi level alignment in simple molecular electronic systems
John K. Tomfohr (2002)
Amine-linked single-molecule circuits: systematic trends across molecular families.
M. Hybertsen (2008)
Preparation of covalent long-chain trialkylstannyl and trialkylsilyl salts and an examination of their adsorption on gold.
D. Khobragade (2010)
Thermoelectric measurements using different tips in atomic force microscopy
S. S. Kushvaha (2011)
Complex thermoelectric materials.
G. Snyder (2008)
Electron transmission through molecules and molecular interfaces.
A. Nitzan (2001)
Contact chemistry and single-molecule conductance: a comparison of phosphines, methyl sulfides, and amines.
Y. S. Park (2007)
Density-functional method for nonequilibrium electron transport
M. Brandbyge (2002)
Role of the exchange-correlation potential in ab initio electron transport calculations.
S. Ke (2007)
Engineering the thermopower of C60 molecular junctions.
C. Evangeli (2013)
Thermoelectricity in Semiconductor Nanostructures
A. Majumdar (2004)
Thermoelectric effect in molecular electronics
M. Paulsson (2003)
Thermopower of amine-gold-linked aromatic molecular junctions from first principles.
S. Y. Quek (2011)
Self-interaction errors in density-functional calculations of electronic transport.
C. Toher (2005)
Measurement of voltage-dependent electronic transport across amine-linked single-molecular-wire junctions.
J. R. Widawsky (2009)
Conserving GW scheme for nonequilibrium quantum transport in molecular contacts
K. Thygesen (2008)
Electron Transport in Molecular Wire Junctions
A. Nitzan (2003)
Single-molecule circuits with well-defined molecular conductance.
L. Venkataraman (2006)
Colloquium: Heat flow and thermoelectricity in atomic and molecular junctions
Y. Dubi (2011)
Charge transport in single Au / alkanedithiol / Au junctions: coordination geometries and conformational degrees of freedom.
C. Li (2008)
Electronic transport in mesoscopic systems
S. Datta (1995)
In situ formation of highly conducting covalent Au-C contacts for single-molecule junctions.
Z-L Cheng (2011)
Formation and evolution of single-molecule junctions.
M. Kamenetska (2009)
Highly conducting π-conjugated molecular junctions covalently bonded to gold electrodes.
Wen-Bo Chen (2011)
Measurement of Single-Molecule Resistance by Repeated Formation of Molecular Junctions
B. Xu (2003)
Renormalization of molecular quasiparticle levels at metal-molecule interfaces: trends across binding regimes.
K. Thygesen (2009)
Probing the chemistry of molecular heterojunctions using thermoelectricity.
K. Baheti (2008)
Simultaneous determination of conductance and thermopower of single molecule junctions.
J. R. Widawsky (2012)
Generalized Gradient Approximation Made Simple.
Thermoelectricity in Molecular Junctions
P. Reddy (2007)
Identifying the length dependence of orbital alignment and contact coupling in molecular heterojunctions.
J. Malen (2009)
Renormalization of molecular electronic levels at metal-molecule interfaces.
J. Neaton (2006)
Dynamical corrections to the DFT-LDA electron conductance in nanoscale systems.
N. Sai (2005)
Length dependence of frontier orbital alignment in aromatic molecular junctions
A. Tan (2012)
Effect of length and contact chemistry on the electronic structure and thermoelectric properties of molecular junctions.
A. Tan (2011)
The SIESTA method for ab initio order-N materials simulation
J. M. Soler (2001)
Conductance of molecular wires and transport calculations based on density-functional theory
F. Evers (2004)
Fundamentals of energy transport, energy conversion, and thermal properties in organic-inorganic heterojunctions
Jonathan A. Malen (2010)
This paper is referenced by
Electrically transmissive alkyne-anchored monolayers on gold.
L. Herrer (2019)
Perspective: Thermal and thermoelectric transport in molecular junctions
L. Cui (2017)
Investigation on Single-Molecule Junctions Based on Current–Voltage Characteristics
Y. Isshiki (2018)
Excellent thermoelectric performance in weak-coupling molecular junctions with electrode doping and electrochemical gating
Dan Wu (2020)
Proton-triggered switch based on a molecular transistor with edge-on gate† †Electronic supplementary information (ESI) available: XPS spectra, contact angle results, UV-Vis spectra, 1H-NMR spectra, STM-BJ results. See DOI: 10.1039/c6sc00152a
Lianwei Li (2016)
Structure-Property Relationships in Atomic-Scale Junctions: Histograms and Beyond.
M. Hybertsen (2016)
Roles of vacuum tunnelling and contact mechanics in single-molecule thermopower
M. Tsutsui (2017)
Quantum-interference-enhanced thermoelectricity in single molecules and molecular films
C. Lambert (2016)
Oligoyne Molecular Junctions for Efficient Room Temperature Thermoelectric Power Generation.
Hatef Sadeghi (2015)
Features of superexchange nonresonant tunneling conductance in anchored molecular wires
É. G. Petrov (2019)
Thermoelectricity in molecular junctions with harmonic and anharmonic modes
B. Agarwalla (2015)
Controlling the Thermoelectric Properties of Thiophene-Derived Single-Molecule Junctions
W. Chang (2014)
Thermoelectric efficiency of single-molecule junctions with long molecular linkers.
N. Zimbovskaya (2018)
Possible Routes for Efficient Thermo-Electric Energy Conversion in a Molecular Junction.
S. Chakraborty (2019)
Voltage Dependence of Molecule–Electrode Coupling in Biased Molecular Junctions
Zhenfei Liu (2017)
Thermoelectric properties of fullerene-based junctions: a first-principles study.
R. Wang (2016)
Temperature Dependence of Conductance and Plateau Length for Single-Molecule Junctions Formed with Silver Electrodes
P. Yoo (2014)
Spatially resolved, substrate-induced rectification in C60 bilayers on copper
J. Smerdon (2017)
End-Group Influence on Frontier Molecular Orbital Reorganization and Thermoelectric Properties of Molecular Junctions
Janakiraman Balachandran (2013)
Can Seebeck coefficient identify quantum interference in molecular conduction
Lena Simine (2014)
Molecular length dictates the nature of charge carriers in single-molecule junctions of oxidized oligothiophenes.
Emma J. Dell (2015)
Structure–thermopower relationships in molecular thermoelectrics
S. Park (2019)
Photoswitching Molecular Junctions: Platforms and Electrical Properties.
Young-sang Kim (2020)
Unsupervised feature recognition in single-molecule break junction data.
A. Magyarkuti (2020)
Single-molecule junctions: thermoelectricity at the gate.
J. Neaton (2014)
Single-molecule electronics: from chemical design to functional devices.
L. Sun (2014)
Thermoelectric efficiency of molecular junctions.
C. Perroni (2016)
Influence of Material Structure on Thermoelectric Properties of Atomic Scale Systems.
Janakiraman Balachandran (2014)
A Novel Way to Enhance the Thermoelectric Efficiency of Carbon Nanotube through Cobaltocene‐decamethyl Cobaltocene Encapsulation
S. Koley (2020)
Heat dissipation and its relation to molecular orbital energies in single-molecule junctions
Y. Naimi (2014)
Determination of energy level alignment and coupling strength in 4,4'-bipyridine single-molecule junctions.
T. Kim (2014)
Thermal and Thermoelectric Properties of Molecular Junctions
Kun Wang (2020)See more