Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids

Randel, Jason C.; Niestemski, Francis C.; Botello-Mendez, Andrés R.; Mar, Warren; Ndabashimiye, Georges; Melinte, Sorin; Dahl, Jeremy E.  P.; Carlson, Robert M.  K.; Butova, Ekaterina D.; Fokin, Andrey A.; Schreiner, Peter R.; Charlier, Jean-Christophe; Manoharan, Hari C.

doi:10.1038/ncomms5877

Title: Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids

Journal Article · Tue Sep 09 00:00:00 EDT 2014 · Nature Communications

DOI:https://doi.org/10.1038/ncomms5877· OSTI ID:1623958

Randel, Jason C. ^[1]; Niestemski, Francis C. ^[2]; Botello-Mendez, Andrés R. ^[3]; Mar, Warren ^[4]; Ndabashimiye, Georges ^[1]; Melinte, Sorin ^[5]; Dahl, Jeremy E. P. ^[6]; Carlson, Robert M. K. ^[6]; Butova, Ekaterina D. ^[7]; Fokin, Andrey A. ^[8]; Schreiner, Peter R. ^[7]; Charlier, Jean-Christophe ^[3]; Manoharan, Hari C. ^[2]

SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences; Stanford Univ., CA (United States). Dept. of Applied Physics
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences; Stanford Univ., CA (United States). Dept. of Physics
Universite Catholique de Louvain, Louvain-la-Neuve (Belgium). Inst. of Condensed Matter and Nanosciences
Stanford Univ., CA (United States). Dept. of Electrical Engineering
Universite Catholique de Louvain, Louvain-la-Neuve (Belgium). Inst. of Information and Communication Technologies, Electronics and Applied Mathematics
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences
Justus-Liebig Univ., Giessen (Germany). Inst. of Organic Chemistry
Justus-Liebig Univ., Giessen (Germany). Inst. of Organic Chemistry; Kiev Polytechnic Inst. (Ukraine)

The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p–n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane–C60 conjugate. By linking both sp3 (diamondoid) and sp2 (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by lowtemperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane–C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1623958

Journal Information:: Nature Communications, Vol. 5, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (31)

Tuning fulleride electronic structure and molecular ordering via variable layer index Wang, Yayu; Yamachika, Ryan; Wachowiak, Andre Nature Materials, Vol. 7, Issue 3, p. 194-197 https://doi.org/10.1038/nmat2100	journal	January 2008
Fullerene-Based Anchoring Groups for Molecular Electronics Martin, Christian A.; Ding, Dapeng; Sørensen, Jakob Kryger Journal of the American Chemical Society, Vol. 130, Issue 40 https://doi.org/10.1021/ja804699a	journal	October 2008
Structures and Displacement of 1-Adamantanethiol Self-Assembled Monolayers on Au{111} Dameron, Arrelaine A.; Charles, Lyndon F.; Weiss, Paul S. Journal of the American Chemical Society, Vol. 127, Issue 24 https://doi.org/10.1021/ja042621o	journal	June 2005
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
Nanomechanical oscillations in a single-C60 transistor Park, Hongkun; Park, Jiwoong; Lim, Andrew K. L. Nature, Vol. 407, Issue 6800 https://doi.org/10.1038/35024031	journal	September 2000
C60: Buckminsterfullerene Kroto, H. W.; Heath, J. R.; O'Brien, S. C. Nature, Vol. 318, Issue 6042 https://doi.org/10.1038/318162a0	journal	November 1985
Transforming C60 molecules into graphene quantum dots Lu, Jiong; Yeo, Pei Shan Emmeline; Gan, Chee Kwan Nature Nanotechnology, Vol. 6, Issue 4 https://doi.org/10.1038/nnano.2011.30	journal	March 2011
The influence of a single thiol group on the electronic and optical properties of the smallest diamondoid adamantane Landt, Lasse; Staiger, Matthias; Wolter, David The Journal of Chemical Physics, Vol. 132, Issue 2 https://doi.org/10.1063/1.3280388	journal	January 2010
Physical principles of the single- $C_{60}$ transistor effect Joachim, C.; Gimzewski, J. K.; Tang, H. Physical Review B, Vol. 58, Issue 24 https://doi.org/10.1103/PhysRevB.58.16407	journal	December 1998
The SIESTA method for ab initio order- N materials simulation Soler, José M.; Artacho, Emilio; Gale, Julian D. Journal of Physics: Condensed Matter, Vol. 14, Issue 11 https://doi.org/10.1088/0953-8984/14/11/302	journal	March 2002
Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation Otero, Gonzalo; Biddau, Giulio; Sánchez-Sánchez, Carlos Nature, Vol. 454, Issue 7206 https://doi.org/10.1038/nature07193	journal	August 2008
Superconductivity in a single-C60 transistor Winkelmann, Clemens B.; Roch, Nicolas; Wernsdorfer, Wolfgang Nature Physics, Vol. 5, Issue 12 https://doi.org/10.1038/nphys1433	journal	October 2009
Orientationally Ordered ( $7 \times 7$ ) Superstructure of $C_{60}$ on Au(111) Schull, G.; Berndt, R. Physical Review Letters, Vol. 99, Issue 22 https://doi.org/10.1103/PhysRevLett.99.226105	journal	November 2007
Supramolecular Nanostructuring of Silver Surfaces via Self-Assembly of [60]Fullerene and Porphyrin Modules Bonifazi, D.; Kiebele, A.; Stöhr, M. Advanced Functional Materials, Vol. 17, Issue 7 https://doi.org/10.1002/adfm.200600586	journal	April 2007
Determination of the orientation of $C_{60}$ adsorbed on Au(111) and Ag(111) Altman, Eric I.; Colton, Richard J. Physical Review B, Vol. 48, Issue 24 https://doi.org/10.1103/PhysRevB.48.18244	journal	December 1993
Monochromatic Electron Photoemission from Diamondoid Monolayers Yang, W. L.; Fabbri, J. D.; Willey, T. M. Science, Vol. 316, Issue 5830 https://doi.org/10.1126/science.1141811	journal	June 2007
Simple Preparation of Diamondoid 1,3-Dienes via Oxetane Ring Opening ^§ Fokin, Andrey A.; Butova, Ekaterina D.; Chernish, Lesya V. Organic Letters, Vol. 9, Issue 13 https://doi.org/10.1021/ol070920n	journal	June 2007
Control over Rectification in Supramolecular Tunneling Junctions Wimbush, Kim S.; Reus, William F.; van der Wiel, Wilfred G. Angewandte Chemie International Edition, Vol. 49, Issue 52 https://doi.org/10.1002/anie.201003286	journal	November 2010
Isolation and Structure of Higher Diamondoids, Nanometer-Sized Diamond Molecules Dahl, J. E. Science, Vol. 299, Issue 5603 https://doi.org/10.1126/science.1078239	journal	November 2002
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
Encapsulated C60 in carbon nanotubes Smith, Brian W.; Monthioux, Marc; Luzzi, David E. Nature, Vol. 396, Issue 6709 https://doi.org/10.1038/24521	journal	November 1998
Mechanically controlled molecular orbital alignment in single molecule junctions Bruot, Christopher; Hihath, Joshua; Tao, Nongjian Nature Nanotechnology, Vol. 7, Issue 1 https://doi.org/10.1038/nnano.2011.212	journal	December 2011
Vibronic Spectroscopy of Single C ₆₀ Molecules and Monolayers with the STM ^† Pradhan, Nilay A.; Liu, Ning; Ho, Wilson The Journal of Physical Chemistry B, Vol. 109, Issue 17 https://doi.org/10.1021/jp045289b	journal	May 2005
Heterofullerenes Vostrowsky, Otto; Hirsch, Andreas Chemical Reviews, Vol. 106, Issue 12 https://doi.org/10.1021/cr050561e	journal	December 2006
Blueprinting macromolecular electronics Palma, Carlos-Andres; Samorì, Paolo Nature Chemistry, Vol. 3, Issue 6 https://doi.org/10.1038/nchem.1043	journal	May 2011
Spectroscopy of C ₆₀ single molecules: the role of screening on energy level alignment Fernández Torrente, Isabel; Franke, Katharina J.; Ignacio Pascual, Jose Journal of Physics: Condensed Matter, Vol. 20, Issue 18 https://doi.org/10.1088/0953-8984/20/18/184001	journal	April 2008
Voltage tuning of vibrational mode energies in single-molecule junctions Li, Y.; Doak, P.; Kronik, L. Proceedings of the National Academy of Sciences, Vol. 111, Issue 4 https://doi.org/10.1073/pnas.1320210111	journal	January 2014
Spatially resolved electronic and vibronic properties of single diamondoid molecules Wang, Yayu; Kioupakis, Emmanouil; Lu, Xinghua Nature Materials, Vol. 7, Issue 1 https://doi.org/10.1038/nmat2066	journal	November 2007
Diamonds are a Chemist's Best Friend: Diamondoid Chemistry Beyond Adamantane Schwertfeger, Hartmut; Fokin, Andrey A.; Schreiner, Peter R. Angewandte Chemie International Edition, Vol. 47, Issue 6 https://doi.org/10.1002/anie.200701684	journal	January 2008
Recent advances in submolecular resolution with scanning probe microscopy Gross, Leo Nature Chemistry, Vol. 3, Issue 4 https://doi.org/10.1038/nchem.1008	journal	March 2011
Tunneling spectroscopy of isolated $C_{60}$ molecules in the presence of charging effects Porath, Danny; Levi, Yair; Tarabiah, Moeen Physical Review B, Vol. 56, Issue 15 https://doi.org/10.1103/physrevb.56.9829	journal	October 1997

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[2](1,3)Adamantano[2](2,7)pyrenophane: A Hydrocarbon with a Large Dipole Moment Kahl, Paul; Wagner, J. Philipp; Balestrieri, Ciro Angewandte Chemie, Vol. 128, Issue 32 https://doi.org/10.1002/ange.201602201	journal	March 2016
Transition metal complexes with cage-opened diamondoid tetracyclo[7.3.1.1 ^4,12 .0 ^2,7 ]tetradeca-6.11-diene Valentin, Lars; Henss, Anja; Tkachenko, Boryslav A. Journal of Coordination Chemistry, Vol. 68, Issue 17-18 https://doi.org/10.1080/00958972.2015.1071802	journal	August 2015
[2](1,3)Adamantano[2](2,7)pyrenophane: A Hydrocarbon with a Large Dipole Moment Kahl, Paul; Wagner, J. Philipp; Balestrieri, Ciro Angewandte Chemie International Edition, Vol. 55, Issue 32 https://doi.org/10.1002/anie.201602201	journal	August 2016

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