Controlling the rectification properties of molecular junctions through molecule–electrode coupling

Koepf, Matthieu; Koenigsmann, Christopher; Ding, Wendu; Batra, Arunbah; Negre, Christian F. A.; Venkataraman, Latha; Brudvig, Gary W.; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.

doi:10.1039/C6NR04830G

Title: Controlling the rectification properties of molecular junctions through molecule–electrode coupling

Journal Article · Wed Aug 17 00:00:00 EDT 2016 · Nanoscale

DOI:https://doi.org/10.1039/C6NR04830G· OSTI ID:1338800

Koepf, Matthieu ^[1]; Koenigsmann, Christopher ^[1]; Ding, Wendu ^[1]; Batra, Arunbah ^[2]; Negre, Christian F. A. ^[3]; Venkataraman, Latha ^[2]; Brudvig, Gary W. ^[1]; Batista, Victor S. ^[1]; Schmuttenmaer, Charles A. ^[1]; Crabtree, Robert H. ^[1]

Yale Univ., New Haven, CT (United States)
Columbia Univ., New York, NY (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

The development of molecular components functioning as switches, rectifiers or amplifiers is a great challenge in molecular electronics. A desirable property of such components is functional robustness, meaning that the intrinsic functionality of components must be preserved regardless of the strategy used to integrate them into the final assemblies. Here, this issue is investigated for molecular diodes based on N-phenylbenzamide (NPBA) backbones. The transport properties of molecular junctions derived from NPBA are characterized while varying the nature of the functional groups interfacing the backbone and the gold electrodes required for break-junction measurements. Furthermore, combining experimental and theoretical methods, it is shown that at low bias (<0.85 V) transport is determined by the same frontier molecular orbital originating from the NPBA core, regardless of the anchoring group employed. The magnitude of rectification, however, is strongly dependent on the strength of the electronic coupling at the gold–NPBA interface and on the spatial distribution of the local density of states of the dominant transport channel of the molecular junction.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-06NA25396; SC0001059

OSTI ID:: 1338800

Report Number(s):: LA-UR-16-21864; NANOHL

Journal Information:: Nanoscale, Vol. 8, Issue 36; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 29 works

Citation information provided by
Web of Science

References (32)

A brief history of molecular electronics Ratner, Mark Nature Nanotechnology, Vol. 8, Issue 6 https://doi.org/10.1038/nnano.2013.110	journal	June 2013
Electronics using hybrid-molecular and mono-molecular devices Joachim, C.; Gimzewski, J. K.; Aviram, A. Nature, Vol. 408, Issue 6812, p. 541-548 https://doi.org/10.1038/35046000	journal	November 2000
Molecular Electronics Heath, James R. Annual Review of Materials Research, Vol. 39, Issue 1 https://doi.org/10.1146/annurev-matsci-082908-145401	journal	August 2009
Unimolecular Electronics Metzger, Robert M. Chemical Reviews, Vol. 115, Issue 11 https://doi.org/10.1021/cr500459d	journal	May 2015
Toggled with electrical current van der Molen, Sense Jan Nature Nanotechnology, Vol. 8, Issue 9 https://doi.org/10.1038/nnano.2013.172	journal	September 2013
Linker Rectifiers for Covalent Attachment of Transition-Metal Catalysts to Metal-Oxide Surfaces Ding, Wendu; Negre, Christian F. A.; Palma, Julio L. ChemPhysChem, Vol. 15, Issue 6 https://doi.org/10.1002/cphc.201400063	journal	March 2014
Single Molecule Rectification Induced by the Asymmetry of a Single Frontier Orbital Ding, Wendu; Negre, Christian F. A.; Vogt, Leslie Journal of Chemical Theory and Computation, Vol. 10, Issue 8 https://doi.org/10.1021/ct5004687	journal	July 2014
Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N -Phenylbenzamide Ding, Wendu; Koepf, Matthieu; Koenigsmann, Christopher Journal of Chemical Theory and Computation, Vol. 11, Issue 12 https://doi.org/10.1021/acs.jctc.5b00823	journal	November 2015
Crucial Role of Nuclear Dynamics for Electron Injection in a Dye–Semiconductor Complex Monti, Adriano; Negre, Christian F. A.; Batista, Victor S. The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00876	journal	June 2015
Measurement of Single-Molecule Resistance by Repeated Formation of Molecular Junctions Xu, B. Science, Vol. 301, Issue 5637 https://doi.org/10.1126/science.1087481	journal	August 2003
Formation and Evolution of Single-Molecule Junctions Kamenetska, M.; Koentopp, M.; Whalley, A. C. Physical Review Letters, Vol. 102, Issue 12 https://doi.org/10.1103/PhysRevLett.102.126803	journal	March 2009
Promising anchoring groups for single-molecule conductance measurements Kaliginedi, Veerabhadrarao; V. Rudnev, Alexander; Moreno-García, Pavel Phys. Chem. Chem. Phys., Vol. 16, Issue 43 https://doi.org/10.1039/C4CP03605K	journal	January 2014
Tuning Rectification in Single-Molecular Diodes Batra, Arunabh; Darancet, Pierre; Chen, Qishui Nano Letters, Vol. 13, Issue 12 https://doi.org/10.1021/nl403698m	journal	November 2013
A single-molecule diode Elbing, M.; Ochs, R.; Koentopp, M. Proceedings of the National Academy of Sciences, Vol. 102, Issue 25 https://doi.org/10.1073/pnas.0408888102	journal	June 2005
Rectification and stability of a single molecular diode with controlled orientation Díez-Pérez, Ismael; Hihath, Joshua; Lee, Youngu Nature Chemistry, Vol. 1, Issue 8 https://doi.org/10.1038/nchem.392	journal	October 2009
Molecular Electronics Cuevas, Juan Carlos; Scheer, Elke World Scientific Series in Nanoscience and Nanotechnology, Vol. 1 https://doi.org/10.1142/7434	book	January 2010
Measurement of voltage-dependent electronic transport across amine-linked single-molecular-wire junctions Widawsky, J. R.; Kamenetska, M.; Klare, J. Nanotechnology, Vol. 20, Issue 43 https://doi.org/10.1088/0957-4484/20/43/434009	journal	October 2009
Density-functional method for nonequilibrium electron transport Brandbyge, Mads; Mozos, José-Luis; Ordejón, Pablo Physical Review B, Vol. 65, Issue 16, Article No. 165401 https://doi.org/10.1103/PhysRevB.65.165401	journal	March 2002
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Trimethyltin-Mediated Covalent Gold–Carbon Bond Formation Batra, Arunabh; Kladnik, Gregor; Gorjizadeh, Narjes Journal of the American Chemical Society, Vol. 136, Issue 36 https://doi.org/10.1021/ja5061406	journal	September 2014
Highly Conducting π-Conjugated Molecular Junctions Covalently Bonded to Gold Electrodes Chen, Wenbo; Widawsky, Jonathan R.; Vázquez, Héctor Journal of the American Chemical Society, Vol. 133, Issue 43 https://doi.org/10.1021/ja208020j	journal	November 2011
In situ formation of highly conducting covalent Au–C contacts for single-molecule junctions Cheng, Z. -L.; Skouta, R.; Vazquez, H. Nature Nanotechnology, Vol. 6, Issue 6 https://doi.org/10.1038/nnano.2011.66	journal	May 2011
Dependence of single-molecule junction conductance on molecular conformation Venkataraman, Latha; Klare, Jennifer E.; Nuckolls, Colin Nature, Vol. 442, Issue 7105 https://doi.org/10.1038/nature05037	journal	August 2006
Amine−Gold Linked Single-Molecule Circuits: Experiment and Theory Quek, Su Ying; Venkataraman, Latha; Choi, Hyoung Joon Nano Letters, Vol. 7, Issue 11 https://doi.org/10.1021/nl072058i	journal	November 2007
Transmission eigenchannels from nonequilibrium Green’s functions Paulsson, Magnus; Brandbyge, Mads Physical Review B, Vol. 76, Issue 11 https://doi.org/10.1103/PhysRevB.76.115117	journal	September 2007
Theory of Rectification in Tour Wires: The Role of Electrode Coupling Taylor, Jeremy; Brandbyge, Mads; Stokbro, Kurt Physical Review Letters, Vol. 89, Issue 13 https://doi.org/10.1103/PhysRevLett.89.138301	journal	September 2002
Enhancing thermoelectric properties of single-walled carbon nanotubes using halide compounds at room temperature and above. Kumanek, Bogumiła; Stando, Grzegorz; Stando, Paweł Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.68746	text	January 2021
Unimolecular electronics Metzger, Robert M. Journal of Materials Chemistry, Vol. 18, Issue 37 https://doi.org/10.1039/b802804b	journal	January 2008
Formation and Evolution of Single Molecule Junctions Kamenetska, M.; Koentopp, M.; Whalley, A. C. arXiv https://doi.org/10.48550/arxiv.0901.1134	text	January 2009
Density functional method for nonequilibrium electron transport Brandbyge, Mads; Mozos, Jose-Luis; Ordejon, Pablo arXiv https://doi.org/10.48550/arxiv.cond-mat/0110650	text	January 2001
Dependence of Single Molecule Junction Conductance on Molecular Conformation Venkataraman, Latha; Klare, Jennifer E.; Nuckolls, Colin arXiv https://doi.org/10.48550/arxiv.cond-mat/0607836	text	January 2006
Transmission eigenchannels from non-equilibrium Green's functions Paulsson, Magnus; Brandbyge, Mads arXiv https://doi.org/10.48550/arxiv.cond-mat/0702295	text	January 2007

Cited By (9)

The maximum rectification ratio of pyrene-based molecular devices: a systematic study Jamali, M. Farid; Soleimani, H. Rahimpour; Tagani, M. Bagheri Journal of Computational Electronics, Vol. 18, Issue 2 https://doi.org/10.1007/s10825-019-01307-5	journal	February 2019
Control of the rectifying effect and direction by redox asymmetry in Rh ₂ -based molecular diodes Bu, Donglei; Xiong, Yingqi; Tan, Ying Ning Chemical Communications, Vol. 54, Issue 29 https://doi.org/10.1039/c8cc02062k	journal	January 2018
Quo vadis, unimolecular electronics? Metzger, Robert Melville Nanoscale, Vol. 10, Issue 22 https://doi.org/10.1039/c8nr01905c	journal	January 2018
A ruthenium-based plasmonic hybrid photocatalyst for aqueous carbon dioxide conversion with a high reaction rate and selectivity Jun, Hwiseok; Choi, Shinyoung; Yang, Moon Young Journal of Materials Chemistry A, Vol. 7, Issue 29 https://doi.org/10.1039/c9ta05880j	journal	January 2019
A real-time extension of density matrix embedding theory for non-equilibrium electron dynamics Kretchmer, Joshua S.; Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 148, Issue 5 https://doi.org/10.1063/1.5012766	journal	February 2018
Molecular modelling and simulation for the design of molecular diodes using density functional theory Siddiqui, Shamoon Ahmad Molecular Simulation, Vol. 46, Issue 6 https://doi.org/10.1080/08927022.2020.1726913	journal	February 2020
Naphthalene and its BN analogues in the weak coupling regime: a general rule for their I-V characteristics Pati, Y. Anusooya Materials Research Express, Vol. 6, Issue 11 https://doi.org/10.1088/2053-1591/ab48c8	journal	September 2019
Molecular modelling and simulation for the design of molecular diodes using density functional theory Siddiqui, Shamoon Ahmad Taylor & Francis https://doi.org/10.6084/m9.figshare.11854911.v1	text	January 2020
Molecular modelling and simulation for the design of molecular diodes using density functional theory Siddiqui, Shamoon Ahmad Taylor & Francis https://doi.org/10.6084/m9.figshare.11854911	text	January 2020

Similar Records

Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives

Journal Article · Thu Jun 30 00:00:00 EDT 2016 · New Journal of Chemistry · OSTI ID:1338800

Koenigsmann, Christopher; Ding, Wendu; Koepf, Matthieu; +7 more

Measurement and understanding of single-molecule break junction rectification caused by asymmetric contacts

Journal Article · Thu Aug 07 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:1338800

Wang, Kun; Zhou, Jianfeng; Hamill, Joseph M.; +1 more

Molecular Junctions: Control of the Energy Gap Achieved by a Pinning Effect

Journal Article · Tue Jan 17 00:00:00 EST 2017 · Journal of Physical Chemistry. C · OSTI ID:1338800

Van Dyck, Colin; Ratner, Mark A.

Related Subjects

36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY
material Science
organic chemistry
single molecule
rectification
STM-BJ
molecular diode
anchoring groups

Title: Controlling the rectification properties of molecular junctions through molecule–electrode coupling

Citation Formats

References (32)

Cited By (9)

Similar Records

Related Subjects