Online citations, reference lists, and bibliographies.
← 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

Cite This
Download PDF
Analyze on Scholarcy
Share
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
10.1021/JZ300668C
End-Group Induced Charge Transfer in Molecular Junctions: Effect on Electronic-Structure and Thermopower
Janakiraman Balachandran (2012)
10.1103/PHYSREVB.65.245105
Complex band structure, decay lengths, and Fermi level alignment in simple molecular electronic systems
John K. Tomfohr (2002)
10.1088/0953-8984/20/37/374115
Amine-linked single-molecule circuits: systematic trends across molecular families.
M. Hybertsen (2008)
10.1021/la101023b
Preparation of covalent long-chain trialkylstannyl and trialkylsilyl salts and an examination of their adsorption on gold.
D. Khobragade (2010)
10.1063/1.3581073
Thermoelectric measurements using different tips in atomic force microscopy
S. S. Kushvaha (2011)
10.1038/nmat2090
Complex thermoelectric materials.
G. Snyder (2008)
10.1146/ANNUREV.PHYSCHEM.52.1.681
Electron transmission through molecules and molecular interfaces.
A. Nitzan (2001)
10.1021/JA0773857
Contact chemistry and single-molecule conductance: a comparison of phosphines, methyl sulfides, and amines.
Y. S. Park (2007)
10.1103/PhysRevB.65.165401
Density-functional method for nonequilibrium electron transport
M. Brandbyge (2002)
10.1063/1.2743004
Role of the exchange-correlation potential in ab initio electron transport calculations.
S. Ke (2007)
10.1021/nl400579g
Engineering the thermopower of C60 molecular junctions.
C. Evangeli (2013)
10.1126/SCIENCE.1093164
Thermoelectricity in Semiconductor Nanostructures
A. Majumdar (2004)
10.1103/PhysRevB.67.241403
Thermoelectric effect in molecular electronics
M. Paulsson (2003)
10.1021/nn102604g
Thermopower of amine-gold-linked aromatic molecular junctions from first principles.
S. Y. Quek (2011)
10.1103/PhysRevLett.95.146402
Self-interaction errors in density-functional calculations of electronic transport.
C. Toher (2005)
10.1088/0957-4484/20/43/434009
Measurement of voltage-dependent electronic transport across amine-linked single-molecular-wire junctions.
J. R. Widawsky (2009)
10.1103/PhysRevB.77.115333
Conserving GW scheme for nonequilibrium quantum transport in molecular contacts
K. Thygesen (2008)
10.1126/SCIENCE.1081572
Electron Transport in Molecular Wire Junctions
A. Nitzan (2003)
10.1021/nl052373+
Single-molecule circuits with well-defined molecular conductance.
L. Venkataraman (2006)
10.1103/REVMODPHYS.83.131
Colloquium: Heat flow and thermoelectricity in atomic and molecular junctions
Y. Dubi (2011)
10.1021/JA0762386
Charge transport in single Au / alkanedithiol / Au junctions: coordination geometries and conformational degrees of freedom.
C. Li (2008)
10.1063/1.2807624
Electronic transport in mesoscopic systems
S. Datta (1995)
10.1038/nnano.2011.66
In situ formation of highly conducting covalent Au-C contacts for single-molecule junctions.
Z-L Cheng (2011)
10.1103/PhysRevLett.102.126803
Formation and evolution of single-molecule junctions.
M. Kamenetska (2009)
10.1021/ja208020j
Highly conducting π-conjugated molecular junctions covalently bonded to gold electrodes.
Wen-Bo Chen (2011)
10.1126/SCIENCE.1087481
Measurement of Single-Molecule Resistance by Repeated Formation of Molecular Junctions
B. Xu (2003)
10.1103/PhysRevLett.102.046802
Renormalization of molecular quasiparticle levels at metal-molecule interfaces: trends across binding regimes.
K. Thygesen (2009)
10.1021/nl072738l
Probing the chemistry of molecular heterojunctions using thermoelectricity.
K. Baheti (2008)
10.1021/nl203634m
Simultaneous determination of conductance and thermopower of single molecule junctions.
J. R. Widawsky (2012)
10.1103/PHYSREVLETT.77.3865
Generalized Gradient Approximation Made Simple.
Perdew (1996)
10.1126/science.1137149
Thermoelectricity in Molecular Junctions
P. Reddy (2007)
10.1021/nl803814f
Identifying the length dependence of orbital alignment and contact coupling in molecular heterojunctions.
J. Malen (2009)
10.1103/PhysRevLett.97.216405
Renormalization of molecular electronic levels at metal-molecule interfaces.
J. Neaton (2006)
10.1103/PhysRevLett.94.186810
Dynamical corrections to the DFT-LDA electron conductance in nanoscale systems.
N. Sai (2005)
10.1063/1.4769986
Length dependence of frontier orbital alignment in aromatic molecular junctions
A. Tan (2012)
10.1021/ja202178k
Effect of length and contact chemistry on the electronic structure and thermoelectric properties of molecular junctions.
A. Tan (2011)
10.1088/0953-8984/14/11/302
The SIESTA method for ab initio order-N materials simulation
J. M. Soler (2001)
10.1103/PHYSREVB.69.235411
Conductance of molecular wires and transport calculations based on density-functional theory
F. Evers (2004)
10.1016/J.CPLETT.2010.03.028
Fundamentals of energy transport, energy conversion, and thermal properties in organic-inorganic heterojunctions
Jonathan A. Malen (2010)



This paper is referenced by
10.1039/c8nr10464f
Electrically transmissive alkyne-anchored monolayers on gold.
L. Herrer (2019)
10.1063/1.4976982
Perspective: Thermal and thermoelectric transport in molecular junctions
L. Cui (2017)
10.3390/mi9020067
Investigation on Single-Molecule Junctions Based on Current–Voltage Characteristics
Y. Isshiki (2018)
10.1007/s11433-019-1528-y
Excellent thermoelectric performance in weak-coupling molecular junctions with electrode doping and electrochemical gating
Dan Wu (2020)
10.1039/c6sc00152a
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)
10.1021/acs.accounts.6b00004
Structure-Property Relationships in Atomic-Scale Junctions: Histograms and Beyond.
M. Hybertsen (2016)
10.1038/srep44276
Roles of vacuum tunnelling and contact mechanics in single-molecule thermopower
M. Tsutsui (2017)
10.1016/J.CRHY.2016.08.003
Quantum-interference-enhanced thermoelectricity in single molecules and molecular films
C. Lambert (2016)
10.1021/acs.nanolett.5b03033
Oligoyne Molecular Junctions for Efficient Room Temperature Thermoelectric Power Generation.
Hatef Sadeghi (2015)
10.1063/1.5124386
Features of superexchange nonresonant tunneling conductance in anchored molecular wires
É. G. Petrov (2019)
10.3762/bjnano.6.218
Thermoelectricity in molecular junctions with harmonic and anharmonic modes
B. Agarwalla (2015)
10.1021/CM504254N
Controlling the Thermoelectric Properties of Thiophene-Derived Single-Molecule Junctions
W. Chang (2014)
10.1088/1361-648X/aacd3a
Thermoelectric efficiency of single-molecule junctions with long molecular linkers.
N. Zimbovskaya (2018)
10.1002/cphc.201900030
Possible Routes for Efficient Thermo-Electric Energy Conversion in a Molecular Junction.
S. Chakraborty (2019)
10.1021/ACS.JPCC.7B05567
Voltage Dependence of Molecule–Electrode Coupling in Biased Molecular Junctions
Zhenfei Liu (2017)
10.1039/C6CP04339A
Thermoelectric properties of fullerene-based junctions: a first-principles study.
R. Wang (2016)
10.1021/JP510053G
Temperature Dependence of Conductance and Plateau Length for Single-Molecule Junctions Formed with Silver Electrodes
P. Yoo (2014)
10.1063/1.4975795
Spatially resolved, substrate-induced rectification in C60 bilayers on copper
J. Smerdon (2017)
10.1021/JZ401678M
End-Group Influence on Frontier Molecular Orbital Reorganization and Thermoelectric Properties of Molecular Junctions
Janakiraman Balachandran (2013)
10.1021/JP512648F
Can Seebeck coefficient identify quantum interference in molecular conduction
Lena Simine (2014)
10.1038/nchem.2160
Molecular length dictates the nature of charge carriers in single-molecule junctions of oxidized oligothiophenes.
Emma J. Dell (2015)
10.1039/C9TA03358K
Structure–thermopower relationships in molecular thermoelectrics
S. Park (2019)
10.1002/cphc.202000564
Photoswitching Molecular Junctions: Platforms and Electrical Properties.
Young-sang Kim (2020)
10.1039/D0NR00467G
Unsupervised feature recognition in single-molecule break junction data.
A. Magyarkuti (2020)
10.1038/nnano.2014.256
Single-molecule junctions: thermoelectricity at the gate.
J. Neaton (2014)
10.1039/c4cs00143e
Single-molecule electronics: from chemical design to functional devices.
L. Sun (2014)
10.1088/0953-8984/28/37/373001
Thermoelectric efficiency of molecular junctions.
C. Perroni (2016)
Influence of Material Structure on Thermoelectric Properties of Atomic Scale Systems.
Janakiraman Balachandran (2014)
10.1002/slct.201904866
A Novel Way to Enhance the Thermoelectric Efficiency of Carbon Nanotube through Cobaltocene‐decamethyl Cobaltocene Encapsulation
S. Koley (2020)
10.1002/pssb.201552020
Heat dissipation and its relation to molecular orbital energies in single-molecule junctions
Y. Naimi (2014)
10.1021/nl404143v
Determination of energy level alignment and coupling strength in 4,4'-bipyridine single-molecule junctions.
T. Kim (2014)
10.1002/adfm.201904534
Thermal and Thermoelectric Properties of Molecular Junctions
Kun Wang (2020)
See more
Semantic Scholar Logo Some data provided by SemanticScholar