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

Van Dyck, Colin; Ratner, Mark A.

doi:10.1021/acs.jpcc.6b07855

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

DOI:https://doi.org/10.1021/acs.jpcc.6b07855· OSTI ID:1388636

^[1]; Ratner, Mark A. ^[1]

Northwestern Univ., Evanston, IL (United States). Chemistry Dept.

Single-molecule junctions are the constitutive components of molecular electronics circuits. For any potential application, the energy gap in the junction, i.e., the accumulated energy difference between the electrode Fermi level and the two frontier energy levels of the molecule, is a key property. In this study, using the nonequilibrium Green’s function coupled to the density functional theory framework (NEGF-DFT) method, we show that the gap of the molecule inserted between electrodes can differ largely from the gap of the same molecule, at the isolated level. It can be widely compressed by tuning the alignment mechanism at each metal/molecule interface. In the context of molecular rectification, we show that this mechanism relates to the pinning effect. We discuss the different parameters affecting the compression of the gap and its efficiency. Interestingly, we find that the structure both of the molecule and of the anchoring group plays an important role. Finally, we investigate the evolution of these features out-of-equilibrium.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0000989

OSTI ID:: 1388636

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 5 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (72)

Fermi Level Pinning and Orbital Polarization Effects in Molecular Junctions: The Role of Metal Induced Gap States Van Dyck, Colin; Geskin, Victor; Cornil, Jérôme Advanced Functional Materials, Vol. 24, Issue 39 https://doi.org/10.1002/adfm.201400809	journal	August 2014
Energy-Level Alignment at Organic/Metal and Organic/Organic Interfaces Braun, Slawomir; Salaneck, William R.; Fahlman, Mats Advanced Materials, Vol. 21, Issue 14-15, p. 1450-1472 https://doi.org/10.1002/adma.200802893	journal	April 2009
A Bipodal Dicyano Anchor Unit for Single-Molecule Spintronic Devices Tsuji, Yuta; Semoto, Takayuki; Yoshizawa, Kazunari ChemPhysChem, Vol. 14, Issue 11 https://doi.org/10.1002/cphc.201300136	journal	June 2013
Revealing the Role of Anchoring Groups in the Electrical Conduction Through Single-Molecule Junctions Zotti, Linda A.; Kirchner, Thomas; Cuevas, Juan-Carlos Small, Vol. 6, Issue 14 https://doi.org/10.1002/smll.200902227	journal	June 2010
Nanoscale device modeling: the Green’s function method Datta, Supriyo Superlattices and Microstructures, Vol. 28, Issue 4 https://doi.org/10.1006/spmi.2000.0920	journal	October 2000
Ab-initio Non-Equilibrium Green’s Function Formalism for Calculating Electron Transport in Molecular Devices Stokbro, K.; Taylor, J.; Brandbyge, M. Introducing Molecular Electronics https://doi.org/10.1007/3-540-31514-4_5	book	January 2005
Molecular rectifiers Aviram, Arieh; Ratner, Mark A. Chemical Physics Letters, Vol. 29, Issue 2 https://doi.org/10.1016/0009-2614(74)85031-1	journal	November 1974
First-principles based matrix Green's function approach to molecular electronic devices: general formalism Xue, Yongqiang; Datta, Supriyo; Ratner, Mark A. Chemical Physics, Vol. 281, Issue 2-3 https://doi.org/10.1016/S0301-0104(02)00446-9	journal	August 2002
Unimolecular rectifiers: Present status Metzger, Robert M. Chemical Physics, Vol. 326, Issue 1 https://doi.org/10.1016/j.chemphys.2006.02.026	journal	July 2006
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Electrical transmission of molecular bridges Remacle, F.; Levine, R. D. Chemical Physics Letters, Vol. 383, Issue 5-6 https://doi.org/10.1016/j.cplett.2003.11.072	journal	January 2004
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
Impact of Anchoring Groups on Ballistic Transport: Single Molecule vs Monolayer Junctions Obersteiner, Veronika; Egger, David A.; Zojer, Egbert The Journal of Physical Chemistry C, Vol. 119, Issue 36 https://doi.org/10.1021/acs.jpcc.5b06110	journal	August 2015
Impact of Electrode Density of States on Transport through Pyridine-Linked Single Molecule Junctions Adak, Olgun; Korytár, Richard; Joe, Andrew Y. Nano Letters, Vol. 15, Issue 6 https://doi.org/10.1021/acs.nanolett.5b01195	journal	June 2015
A Molecular Diode with a Statistically Robust Rectification Ratio of Three Orders of Magnitude Yuan, Li; Breuer, Rochus; Jiang, Li Nano Letters, Vol. 15, Issue 8 https://doi.org/10.1021/acs.nanolett.5b02014	journal	July 2015
Large Spatially Resolved Rectification in a Donor–Acceptor Molecular Heterojunction Smerdon, Joseph A.; Giebink, Noel C.; Guisinger, Nathan P. Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.6b00171	journal	March 2016
Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function Xie, Zuoti; Bâldea, Ioan; Smith, Christopher E. ACS Nano, Vol. 9, Issue 8 https://doi.org/10.1021/acsnano.5b01629	journal	July 2015
Visualizing the Role of Molecular Orbitals in Charge Transport through Individual Diarylethene Isomers Reecht, Gaël; Lotze, Christian; Sysoiev, Dmytro ACS Nano, Vol. 10, Issue 11 https://doi.org/10.1021/acsnano.6b06559	journal	October 2016
Predictive DFT-Based Approaches to Charge and Spin Transport in Single-Molecule Junctions and Two-Dimensional Materials: Successes and Challenges Quek, Su Ying; Khoo, Khoong Hong Accounts of Chemical Research, Vol. 47, Issue 11 https://doi.org/10.1021/ar4002526	journal	June 2014
Molecular Electronic Junctions McCreery, Richard L. Chemistry of Materials, Vol. 16, Issue 23 https://doi.org/10.1021/cm049517q	journal	November 2004
Unimolecular Electronics Metzger, Robert M. Chemical Reviews, Vol. 115, Issue 11 https://doi.org/10.1021/cr500459d	journal	May 2015
Single-Molecule Junctions Based on Nitrile-Terminated Biphenyls: A Promising New Anchoring Group Mishchenko, Artem; Zotti, Linda A.; Vonlanthen, David Journal of the American Chemical Society, Vol. 133, Issue 2 https://doi.org/10.1021/ja107340t	journal	January 2011
Molecular Tunnel Junctions Based on π-Conjugated Oligoacene Thiols and Dithiols between Ag, Au, and Pt Contacts: Effect of Surface Linking Group and Metal Work Function Kim, BongSoo; Choi, Seong Ho; Zhu, X. -Y. Journal of the American Chemical Society, Vol. 133, Issue 49 https://doi.org/10.1021/ja207751w	journal	December 2011
Single Molecular Conductance of Tolanes: Experimental and Theoretical Study on the Junction Evolution Dependent on the Anchoring Group Hong, Wenjing; Manrique, David Zsolt; Moreno-García, Pavel Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja209844r	journal	January 2012
Rectifying Electron-Transport Properties through Stacks of Aromatic Molecules Inserted into a Self-Assembled Cage Fujii, Shintaro; Tada, Tomofumi; Komoto, Yuki Journal of the American Chemical Society, Vol. 137, Issue 18 https://doi.org/10.1021/jacs.5b00086	journal	May 2015
Density Functional for Spectroscopy: No Long-Range Self-Interaction Error, Good Performance for Rydberg and Charge-Transfer States, and Better Performance on Average than B3LYP for Ground States Zhao, Yan; Truhlar, Donald G. The Journal of Physical Chemistry A, Vol. 110, Issue 49 https://doi.org/10.1021/jp066479k	journal	December 2006
Theoretical Study of the Electronic and Optical Properties of Photochromic Dithienylethene Derivatives Connected to Small Gold Clusters Perrier, Aurélie; Maurel, François; Aubard, Jean The Journal of Physical Chemistry A, Vol. 111, Issue 39 https://doi.org/10.1021/jp073436a	journal	October 2007
General Performance of Density Functionals Sousa, Sérgio Filipe; Fernandes, Pedro Alexandrino; Ramos, Maria João The Journal of Physical Chemistry A, Vol. 111, Issue 42 https://doi.org/10.1021/jp0734474	journal	October 2007
Structural versus Electrical Functionalization of Oligo(phenylene ethynylene) Diamine Molecular Junctions González, M. Teresa; Zhao, Xiaotao; Manrique, David Zsolt The Journal of Physical Chemistry C, Vol. 118, Issue 37 https://doi.org/10.1021/jp506078a	journal	September 2014
Single-Molecule Resonant Tunneling Diode Perrin, Mickael L.; Galan, Elena; Eelkema, Rienk The Journal of Physical Chemistry C, Vol. 119, Issue 10 https://doi.org/10.1021/jp512803s	journal	February 2015
Theoretical Modeling of Tunneling Barriers in Carbon-Based Molecular Electronic Junctions Kondratenko, Mykola; Stoyanov, Stanislav R.; Gusarov, Sergey The Journal of Physical Chemistry C, Vol. 119, Issue 21 https://doi.org/10.1021/jp5128332	journal	May 2015
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
Optical Modulation of Molecular Conductance Battacharyya, Shreya; Kibel, Ashley; Kodis, Gerdenis Nano Letters, Vol. 11, Issue 7 https://doi.org/10.1021/nl200977c	journal	July 2011
Quantitative Current–Voltage Characteristics in Molecular Junctions from First Principles Darancet, Pierre; Widawsky, Jonathan R.; Choi, Hyoung Joon Nano Letters, Vol. 12, Issue 12 https://doi.org/10.1021/nl3033137	journal	February 2012
Three-Terminal Single-Molecule Junctions Formed by Mechanically Controllable Break Junctions with Side Gating Xiang, Dong; Jeong, Hyunhak; Kim, Dongku Nano Letters, Vol. 13, Issue 6 https://doi.org/10.1021/nl401067x	journal	May 2013
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
Molecular Rectifiers: A New Design Based on Asymmetric Anchoring Moieties Van Dyck, Colin; Ratner, Mark A. Nano Letters, Vol. 15, Issue 3 https://doi.org/10.1021/nl504091v	journal	February 2015
Single-electron transistor of a single organic molecule with access to several redox states Kubatkin, Sergey; Danilov, Andrey; Hjort, Mattias Nature, Vol. 425, Issue 6959 https://doi.org/10.1038/nature02010	journal	October 2003
Observation of molecular orbital gating Song, Hyunwook; Kim, Youngsang; Jang, Yun Hee Nature, Vol. 462, Issue 7276 https://doi.org/10.1038/nature08639	journal	December 2009
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
Photocurrent of a single photosynthetic protein Gerster, Daniel; Reichert, Joachim; Bi, Hai Nature Nanotechnology, Vol. 7, Issue 10 https://doi.org/10.1038/nnano.2012.165	journal	September 2012
Large tunable image-charge effects in single-molecule junctions Perrin, Mickael L.; Verzijl, Christopher J. O.; Martin, Christian A. Nature Nanotechnology, Vol. 8, Issue 4 https://doi.org/10.1038/nnano.2013.26	journal	March 2013
Reflections on charge transport Heimel, Georg; Brédas, Jean-Luc Nature Nanotechnology, Vol. 8, Issue 4 https://doi.org/10.1038/nnano.2013.42	journal	March 2013
Large negative differential conductance in single-molecule break junctions Perrin, Mickael L.; Frisenda, Riccardo; Koole, Max Nature Nanotechnology, Vol. 9, Issue 10 https://doi.org/10.1038/nnano.2014.177	journal	August 2014
Single-molecule diodes with high rectification ratios through environmental control Capozzi, Brian; Xia, Jianlong; Adak, Olgun Nature Nanotechnology, Vol. 10, Issue 6 https://doi.org/10.1038/nnano.2015.97	journal	May 2015
The Molecular Photo-Cell: Quantum Transport and Energy Conversion at Strong Non-Equilibrium Ajisaka, Shigeru; Žunkovič, Bojan; Dubi, Yonatan Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep08312	journal	February 2015
A gate-tunable single-molecule diode Perrin, Mickael L.; Galán, Elena; Eelkema, Rienk Nanoscale, Vol. 8, Issue 16 https://doi.org/10.1039/C6NR00735J	journal	January 2016
Unimolecular electronics Metzger, Robert M. Journal of Materials Chemistry, Vol. 18, Issue 37 https://doi.org/10.1039/b802804b	journal	January 2008
Extending the reliability and applicability of B3LYP Zhang, Igor Ying; Wu, Jianming; Xu, Xin Chemical Communications, Vol. 46, Issue 18 https://doi.org/10.1039/c000677g	journal	January 2010
Photo-modulable molecular transport junctions based on organometallic molecular wires Meng, Fanben; Hervault, Yves-Marie; Norel, Lucie Chemical Science, Vol. 3, Issue 10 https://doi.org/10.1039/c2sc20323e	journal	January 2012
Impact of derivatization on electron transmission through dithienylethene-based photoswitches in molecular junctions Van Dyck, Colin; Geskin, Victor; Kronemeijer, Auke J. Physical Chemistry Chemical Physics, Vol. 15, Issue 12 https://doi.org/10.1039/c3cp44132f	journal	January 2013
Molecular Electronics Heath, James R.; Ratner, Mark A. Physics Today, Vol. 56, Issue 5 https://doi.org/10.1063/1.1583533	journal	May 2003
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Energy level alignment and quantum conductance of functionalized metal-molecule junctions: Density functional theory versus GW calculations Jin, Chengjun; Strange, Mikkel; Markussen, Troels The Journal of Chemical Physics, Vol. 139, Issue 18 https://doi.org/10.1063/1.4829520	journal	November 2013
The physics and chemistry of the Schottky barrier height Tung, Raymond T. Applied Physics Reviews, Vol. 1, Issue 1 https://doi.org/10.1063/1.4858400	journal	January 2014
Simple model of a coherent molecular photocell Ernzerhof, Matthias; Bélanger, Marc-André; Mayou, Didier The Journal of Chemical Physics, Vol. 144, Issue 13 https://doi.org/10.1063/1.4944468	journal	April 2016
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
Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime Sayed, S. Y.; Fereiro, J. A.; Yan, H. Proceedings of the National Academy of Sciences, Vol. 109, Issue 29 https://doi.org/10.1073/pnas.1201557109	journal	June 2012
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Ab initio modeling of quantum transport properties of molecular electronic devices Taylor, Jeremy; Guo, Hong; Wang, Jian Physical Review B, Vol. 63, Issue 24 https://doi.org/10.1103/PhysRevB.63.245407	journal	June 2001
Numerical atomic orbitals for linear-scaling calculations Junquera, Javier; Paz, Óscar; Sánchez-Portal, Daniel Physical Review B, Vol. 64, Issue 23 https://doi.org/10.1103/PhysRevB.64.235111	journal	November 2001
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
Polarization-induced renormalization of molecular levels at metallic and semiconducting surfaces Garcia-Lastra, J. M.; Rostgaard, C.; Rubio, A. Physical Review B, Vol. 80, Issue 24 https://doi.org/10.1103/PhysRevB.80.245427	journal	December 2009
Ab initio study of the thermopower of biphenyl-based single-molecule junctions Bürkle, M.; Zotti, L. A.; Viljas, J. K. Physical Review B, Vol. 86, Issue 11 https://doi.org/10.1103/PhysRevB.86.115304	journal	September 2012
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
Comment on “Generalized Gradient Approximation Made Simple” Zhang, Yingkai; Yang, Weitao Physical Review Letters, Vol. 80, Issue 4 https://doi.org/10.1103/PhysRevLett.80.890	journal	January 1998
Driving Current through Single Organic Molecules Reichert, J.; Ochs, R.; Beckmann, D. Physical Review Letters, Vol. 88, Issue 17 https://doi.org/10.1103/PhysRevLett.88.176804	journal	April 2002
Adsorption of Thiolates to Singly Coordinated Sites on Au(111) Evidenced by Photoelectron Diffraction Kondoh, H.; Iwasaki, M.; Shimada, T. Physical Review Letters, Vol. 90, Issue 6 https://doi.org/10.1103/PhysRevLett.90.066102	journal	February 2003
Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces Neaton, J. B.; Hybertsen, Mark S.; Louie, Steven G. Physical Review Letters, Vol. 97, Issue 21 https://doi.org/10.1103/PhysRevLett.97.216405	journal	November 2006
Conductance viewed as transmission Imry, Yoseph; Landauer, Rolf Reviews of Modern Physics, Vol. 71, Issue 2 https://doi.org/10.1103/RevModPhys.71.S306	journal	March 1999
Architectures for molecular electronic computers. I. Logic structures and an adder designed from molecular electronic diodes Ellenbogen, J. C.; Love, J. C. Proceedings of the IEEE, Vol. 88, Issue 3 https://doi.org/10.1109/5.838115	journal	March 2000
Effects of electronic coupling and electrostatic potential on charge transport in carbon-based molecular electronic junctions McCreery, Richard L. Beilstein Journal of Nanotechnology, Vol. 7 https://doi.org/10.3762/bjnano.7.4	journal	January 2016

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