Online citations, reference lists, and bibliographies.
← Back to Search

Structure Controlled Long-Range Sequential Tunneling In Carbon-Based Molecular Junctions.

Amin Morteza Najarian, R. McCreery
Published 2017 · Chemistry, Medicine

Cite This
Download PDF
Analyze on Scholarcy
Share
Carbon-based molecular junctions consisting of aromatic oligomers between conducting sp2 hybridized carbon electrodes exhibit structure-dependent current densities (J) when the molecular layer thickness (d) exceeds ∼5 nm. All four of the molecular structures examined exhibit an unusual, nonlinear ln J vs bias voltage (V) dependence which is not expected for conventional coherent tunneling or activated hopping mechanisms. All molecules exhibit a weak temperature dependence, with J increasing typically by a factor of 2 over the range of 200-440 K. Fluorene and anthraquinone show linear plots of ln J vs d with nearly identical J values for the range d = 3-10 nm, despite significant differences in their free-molecule orbital energy levels. The observed current densities for anthraquinone, fluorene, nitroazobenzene, and bis-thienyl benzene for d = 7-10 nm show no correlation with occupied (HOMO) or unoccupied (LUMO) molecular orbital energies, contrary to expectations for transport mechanisms based on the offset between orbital energies and the electrode Fermi level. UV-vis absorption spectroscopy of molecular layers bonded to carbon electrodes revealed internal energy levels of the chemisorbed films and also indicated limited delocalization in the film interior. The observed current densities correlate well with the observed UV-vis absorption maxima for the molecular layers, implying a transport mechanism determined by the HOMO-LUMO energy gap. We conclude that transport in carbon-based aromatic molecular junctions is consistent with multistep tunneling through a barrier defined by the HOMO-LUMO gap, and not by charge transport at the electrode interfaces. In effect, interfacial "injection" at the molecule/electrode interfaces is not rate limiting due to relatively strong electronic coupling, and transport is controlled by the "bulk" properties of the molecular layer interior.
This paper references
10.1039/c5nr02225h
Uncovering a law of corresponding states for electron tunneling in molecular junctions.
I. Bâldea (2015)
Bonded Single-Molecule Junctions With Stable and Reversible Photoswitched Conductivity
B. Ma (2016)
10.1002/adma.201504847
Ultrarobust Thin-Film Devices from Self-Assembled Metal-Terpyridine Oligomers.
Zoi Karipidou (2016)
10.1021/ja206619a
All-carbon molecular tunnel junctions.
Haijun Yan (2011)
10.1016/0370-1573(80)90046-0
Temperature dependent electronic conduction in semiconductors
G. G. Roberts (1980)
Robust AllCarbon Molecular Junctions on Flexible or Semi - Transparent Substrates Using “ ProcessFriendly ” Fabrication
A. Morteza Najarian (2016)
10.1021/JP106362Q
Electronic Characteristics and Charge Transport Mechanisms for Large Area Aromatic Molecular Junctions
A. Bergren (2010)
10.1126/science.1156538
Electrical Resistance of Long Conjugated Molecular Wires
Seong Ho Choi (2008)
10.1021/AC034026V
Mono- and multilayer formation by diazonium reduction on carbon surfaces monitored with atomic force microscopy "scratching".
Franklin Anariba (2003)
10.1080/00207216608937891
Electrical Transport in nGe-pGaAs Heterojunctions†
A. R. Riben (1966)
10.1126/science.aaf6298
Covalently bonded single-molecule junctions with stable and reversible photoswitched conductivity
Chuancheng Jia (2016)
10.1021/cr9001275
High-k organic, inorganic, and hybrid dielectrics for low-voltage organic field-effect transistors.
R. Ponce Ortiz (2010)
10.1002/adma.201101129
Electronic transport in organic materials: comparison of band theory with percolation/(variable range) hopping theory.
P. Stallinga (2011)
10.1126/SCIENCE.1059552
Fully Conjugated Porphyrin Tapes with Electronic Absorption Bands That Reach into Infrared
A. Tsuda (2001)
10.1038/NATREVMATS.2016.2
Chemical principles of single-molecule electronics
Timothy A Su (2016)
10.1063/1.881139
Disordered Electronic Systems
B. Altshuler (1988)
10.1038/nnano.2009.176
Molecular electronics with single molecules in solid-state devices.
K. Moth-Poulsen (2009)
10.1002/AELM.201600351
Monitoring of Energy Conservation and Losses in Molecular Junctions through Characterization of Light Emission
O. Ivashenko (2016)
10.1109/JQE.1979.1069942
The physics of semiconductor devices
H. Grubin (1979)
10.1007/978-3-319-48933-9_9
Charge Transport in Disordered Materials
S. Baranovskii (2017)
10.1021/JP210445Y
Statistical Tools for Analyzing Measurements of Charge Transport
W. Reus (2012)
10.1002/adma.201103109
Comparison of the conductance of three types of porphyrin-based molecular wires: β,meso,β-fused tapes, meso-Butadiyne-linked and twisted meso-meso linked oligomers.
Gita Sedghi (2012)
10.1021/AC052244D
Fabrication of optically transparent carbon electrodes by the pyrolysis of photoresist films: approach to single-molecule spectroelectrochemistry.
Sebastian Donner (2006)
10.1002/adma.200901834
Molecules on si: electronics with chemistry.
A. Vilan (2010)
10.1021/acsnano.6b04900
Robust All-Carbon Molecular Junctions on Flexible or Semi-Transparent Substrates Using "Process-Friendly" Fabrication.
Amin Morteza Najarian (2016)
10.1002/tcr.201100006
The merger of electrochemistry and molecular electronics.
R. McCreery (2012)
10.1366/000370207782597094
Ultraviolet—Visible Spectroelectrochemistry of Chemisorbed Molecular Layers on Optically Transparent Carbon Electrodes
Hong Tian (2007)
10.1038/NMAT2401
Highly conductive |[sim]|40-nm-long molecular wires assembled by stepwise incorporation of metal centres
N. Tuccitto (2009)
10.1016/J.MSER.2008.12.001
Energetics of metal–organic interfaces: New experiments and assessment of the field
Jaehyung Hwang (2009)
10.1038/nature04699
Towards molecular electronics with large-area molecular junctions
H. Akkerman (2006)
10.3762/bjnano.7.4
Effects of electronic coupling and electrostatic potential on charge transport in carbon-based molecular electronic junctions
R. McCreery (2016)
10.1139/CJC-2016-0279
Interpretation of molecular device transport calculations
Josh Gibbs (2016)
10.1002/PSSA.19700010306
Thermally assisted tunnelling in dielectric films
G. G. Roberts (1970)
10.1002/adma.201306316
Flexible molecular-scale electronic devices composed of diarylethene photoswitching molecules.
Dongku Kim (2014)
10.1021/acsnano.5b01629
Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function.
Z. Xie (2015)
10.1038/nnano.2011.111
Long-range electron tunnelling in oligo-porphyrin molecular wires
Gita Sedghi (2011)
10.1021/acs.accounts.5b00133
Carbon Electrode-Molecule Junctions: A Reliable Platform for Molecular Electronics.
Chuancheng Jia (2015)
10.1002/ADMA.200802893
Energy‐Level Alignment at Organic/Metal and Organic/Organic Interfaces
S. Braun (2009)
10.1021/am800126v
Anomalous tunneling in carbon/alkane/TiO(2)/gold molecular electronic junctions: energy level alignment at the metal/semiconductor interface.
H. Yan (2009)
10.1021/JP507044N
Hopping Transport and Rectifying Behavior in Long Donor–Acceptor Molecular Wires
L. Luo (2014)
10.1038/nnano.2010.115
'Soft' Au, Pt and Cu contacts for molecular junctions through surface-diffusion-mediated deposition.
Andrew P. Bonifas (2010)
10.1073/pnas.1221643110
Activationless charge transport across 4.5 to 22 nm in molecular electronic junctions
Haijun Yan (2013)
10.1021/acs.chemrev.5b00680
Molecular-Scale Electronics: From Concept to Function.
D. Xiang (2016)
10.1021/ja511592s
Internal photoemission in molecular junctions: parameters for interfacial barrier determinations.
Jerry A Fereiro (2015)
10.1002/ANIE.200703642
Eutectic gallium-indium (EGaIn): a moldable liquid metal for electrical characterization of self-assembled monolayers.
R. Chiechi (2008)
10.1002/adma.201402304
Electronic transport via proteins.
N. Amdursky (2014)
10.1073/pnas.1201557109
Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime
S. Y. Sayed (2012)
10.1021/ja910547c
Transition from tunneling to hopping transport in long, conjugated oligo-imine wires connected to metals.
S. Choi (2010)
10.1021/cr500459d
Unimolecular electronics.
R. Metzger (2015)
Electrochemistry of Organized Monolayers of Thiols and Related Molecules on Electrodes
H O Finklea (1996)
10.1021/acsnano.5b08126
Charge Transport in 4 nm Molecular Wires with Interrupted Conjugation: Combined Experimental and Computational Evidence for Thermally Assisted Polaron Tunneling.
D. Taherinia (2016)
10.1021/JA043279I
Electronic decay constant of carotenoid polyenes from single-molecule measurements.
J. He (2005)
10.1021/CM102402T
Probing hopping conduction in conjugated molecular wires connected to metal electrodes
Liang Luo (2011)
10.1021/nn9012687
From tunneling to hopping: a comprehensive investigation of charge transport mechanism in molecular junctions based on oligo(p-phenylene ethynylene)s.
Q. Lu (2009)
10.1021/nn3006976
Universal temperature crossover behavior of electrical conductance in a single oligothiophene molecular wire.
S. K. Lee (2012)
10.1039/c2cp43516k
A critical perspective on molecular electronic junctions: there is plenty of room in the middle.
R. McCreery (2013)
10.1021/JP5128332
Theoretical Modeling of Tunneling Barriers in Carbon-based Molecular Electronic Junctions
M. Kondratenko (2015)
Eutectic GalliumIndium ( EGaIn ) : A Moldable Liquid Metal for Electrical Characterization of Self - Assembled Monolayers
R. C. Chiechi (2008)
Long - Range Electron Tunnelling in OligoPorphyrin Molecular Wires
G. Sedghi (2011)
10.1021/JA983204C
Electron Transfer at Electrodes through Conjugated “Molecular Wire” Bridges
S. Creager (1999)
10.1002/ADMA.200803541
Charge Transport in Disordered Organic Materials and Its Relevance to Thin‐Film Devices: A Tutorial Review
N. Tessler (2009)
10.1002/PSSA.2210160137
Dark‐current conduction processes in CdS–Cu2S thin‐film photocells
Santo Martinuzzi (1973)



This paper is referenced by
10.1021/acsami.7b19305
Bottom-up, Robust Graphene Ribbon Electronics in All-Carbon Molecular Junctions.
Mustafa Supur (2018)
10.1021/jacs.0c03943
Ion-assisted Resonant Injection and Charge Storage in Carbon-based Molecular Junctions.
Mustafa Supur (2020)
10.1021/ACS.JPCC.8B09978
Orbital Control of Long-Range Transport in Conjugated and Metal-Centered Molecular Electronic Junctions
Ushula M Tefashe (2018)
10.1002/9781119468288.ch1
Nanoelectrochemistry of Adsorption‐Coupled Electron Transfer at Carbon Electrodes
S. Amemiya (2020)
10.1002/aelm.201901416
Molecular Signature and Activationless Transport in Cobalt‐Terpyridine‐Based Molecular Junctions
Quyen van Nguyen (2020)
10.1039/d0cp03700a
Reply to the 'Comment on "Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling"' by R. L. McCreery, S. K. Saxena, M. Supur and U. Tefashe, Phys. Chem. Chem. Phys., 2020, 22, DOI: 10.1039/d0cp02412k.
A. Bergren (2020)
10.1016/J.COELEC.2017.11.017
Electrochemistry does the impossible: Robust and reliable large area molecular junctions
J. Lacroix (2018)
10.1073/pnas.1816956116
Voltage-induced long-range coherent electron transfer through organic molecules
K. Michaeli (2019)
10.1063/1.5145210
Green’s function methods for single molecule junctions
G. Cohen (2020)
10.1039/c9cp03509e
Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling.
C. Van Dyck (2019)
10.1039/C7NH00109F
Nanometric building blocks for robust multifunctional molecular junctions.
D. D. James (2018)
10.1039/d0cp02412k
Comment on "Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling" by C. Van Dyck, A. J. Bergren, V. Mukundan, J. A. Fereiro and G. A. DiLabio, Phys. Chem. Chem. Phys., 2019, 21, 16762.
R. McCreery (2020)
10.1021/acs.jpcc.9b10076
Unipolar Injection and Bipolar Transport in Electroluminescent Ru-Centered Molecular Electronic Junctions
Ushula M Tefashe (2019)
10.1021/acsnano.8b08662
Long-Range Activationless Photostimulated Charge Transport in Symmetric Molecular Junctions.
Amin Morteza Najarian (2019)
10.1002/ADOM.201901053
Light‐Stimulated Charge Transport in Bilayer Molecular Junctions for Photodetection
S. K. Saxena (2019)
10.1002/AELM.201800093
Photocurrent, Photovoltage, and Rectification in Large‐Area Bilayer Molecular Electronic Junctions
S. R. Smith (2018)
Semantic Scholar Logo Some data provided by SemanticScholar