Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids

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

doi:10.1038/ncomms5877

Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

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-C 60 conjugate. By linking both sp 3 (diamondoid) and sp 2 (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 low-temperature 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-C 60 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.

Original language	English
Article number	4877
Journal	Nature Communications
Volume	5
DOIs	https://doi.org/10.1038/ncomms5877
Publication status	Published - 2014
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2014 Macmillan Publishers Limited. All rights reserved.

Funding

This work was primarily supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under contract DE-AC02-76SF00515. Nanomaterials quantum calculations (W.M. and G.N.) were supported by the US National Science Foundation (DMR-1206916). F.C.N. acknowledges support from the Karl van Bibber Fellowship. W.M. acknowledges support from an NDSEG fellowship. A.R.B.-M. acknowledges support from the M. de Merre Prize of Louvain. This research connects to the F.R.S.-FNRS of Belgium and to the ARC projects entitled ‘Graphene StressTronics’ (No 11/16-037) and ‘TINTIN’ (No 09/14-023) sponsored by the Communauté Franc¸aise de Belgique (A.R.B.-M., S.M., J.-C.C.), and computational resources for DFT were provided by the CISM of the Université catholique de Louvain (GREEN and LEMAITRE computers). P.R.S. and E.D.B. were supported through the Deutsche Forschungsgemeinschaft (Germany) through a DFG-NSF grant (CHE-0822112). A.A.F. was supported by the Ministry of Science and Education of Ukraine. We thank W. Clay, T. Devereaux, J. Fabbri, N. Melosh, A. Sorini and Z. X. Shen for discussions.

Funders	Funder number
DFG-NSF	CHE-0822112
Karl van Bibber Fellowship
National Science Foundation	DMR-1206916
U.S. Department of Energy
Directorate for Mathematical and Physical Sciences	1206916
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering	DE-AC02-76SF00515
the Deutsche Forschungsgemeinschaft
Ministry of Education and Science of Ukraine

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Randel, J. C., Niestemski, F. C., Botello-Mendez, A. R., Mar, W., Ndabashimiye, G., Melinte, S., Dahl, J. E. P., Carlson, R. M. K., Butova, E. D., Fokin, A. A., Schreiner, P. R., Charlier, J. C., & Manoharan, H. C. (2014). Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids. Nature Communications, 5, Article 4877. https://doi.org/10.1038/ncomms5877

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title = "Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids",

abstract = "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-C 60 conjugate. By linking both sp 3 (diamondoid) and sp 2 (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 low-temperature 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-C 60 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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AU - Ndabashimiye, Georges

AU - Melinte, Sorin

AU - Dahl, Jeremy E.P.

AU - Carlson, Robert M.K.

AU - Butova, Ekaterina D.

AU - Fokin, Andrey A.

AU - Schreiner, Peter R.

AU - Charlier, Jean Christophe

AU - Manoharan, Hari C.

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AB - 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-C 60 conjugate. By linking both sp 3 (diamondoid) and sp 2 (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 low-temperature 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-C 60 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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Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids

Abstract

Bibliographical note

Funding

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