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Quantum-tunneling-based nanoelectronics has the potential for the miniaturization of electronics toward the sub-5 nm scale. However, the nature of phase-coherent quantum tunneling leads to the rapid decays of the electrical conductance with tunneling transport distance, especially in organic molecule-based nanodevices. In this work, we investigated the conductance of the single-cluster junctions of a series of atomically well-defined silver nanoclusters, with varying sizes from 0.9 to 3.0 nm, using the mechanically controllable break junction (MCBJ) technique combined with quantum transport theory. Our charge transport investigations of these single-cluster junctions revealed that the conductance grows with increasing cluster size. The conductance decay constant was determined to be ∼-0.4 nm, which is of opposite sign to that of organic molecules. Comparison between experiment and theory reveals that although charge transport through the silver single-cluster junctions occurs via phase-coherent tunneling, this is compensated by a rapid decrease in the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap) with size and the increase in the electrode-cluster coupling, which results in their conductance increase up to lengths of ∼3.0 nm. These results demonstrate that such families of nanoclusters provide unique bottom-up building blocks for the fabrication of nanodevices in the sub-5 nm size range.
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http://dx.doi.org/10.1021/jacs.2c05856 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, College of Chemistry and Materials Science, Zhejiang Normal University, 321004, Jinhua, P. R. China.
The recent discovery of frustrated Lewis pairs (FLPs) during the activation of small molecules has inspired extensive research across the full span of chemical science. Owing to the nature of weak interactions, it is experimentally challenging to directly observe and modulate FLP at the molecular scale. Here we design a boron cluster anion building block (BH ) and organic amine cations ([NR], R=-CH, -CH) as the FLP to prove the feasibility of controlling their interaction in the electric double layer (EDL) via an electrochemical strategy.
View Article and Find Full Text PDFJ Am Chem Soc
August 2022
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering & Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University, 361005 Xiamen, China.
Quantum-tunneling-based nanoelectronics has the potential for the miniaturization of electronics toward the sub-5 nm scale. However, the nature of phase-coherent quantum tunneling leads to the rapid decays of the electrical conductance with tunneling transport distance, especially in organic molecule-based nanodevices. In this work, we investigated the conductance of the single-cluster junctions of a series of atomically well-defined silver nanoclusters, with varying sizes from 0.
View Article and Find Full Text PDFNanoscale
August 2021
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University Xiamen, 361005, China.
The control of single atoms offers fundamental insight into understanding the charge transport through single clusters, and the atomic precision of the clusters provides the opportunity to manipulate the charge transport even at the single-atom level. Herein, we designed and investigated the electrical conductance and thermopower of Anderson-type polyoxometalate (POM) clusters with single-atom variation using the scanning tunneling microscopy break-junction (STM-BJ) technique. Our results show the electrical conductance of single clusters can be changed by an order of magnitude by substituting different center-metal atoms, and the electrical conductance of clusters shows different bias-dependence.
View Article and Find Full Text PDFPhys Chem Chem Phys
April 2021
Department of Chemistry, University of California, Riverside, CA 92521, USA. and Materials Science and Engineering Program, University of California, Riverside, CA 92521, USA.
This article reviews the scope of inorganic cluster compounds interrogated in single-molecule break-junction measurements. This body of work lies at the intersection between the fields of inorganic cluster chemistry and single-molecule electronics, where discrete inorganic cluster molecules are used as the active components in molecular electronic circuitry. We explore the breadth of transition metal and main group cluster compounds that have been studied in single-cluster junctions, largely within the context of scanning tunnelling microscopy break-junction (STM-BJ) measurements.
View Article and Find Full Text PDFJ Am Chem Soc
September 2020
Department of Chemistry, Columbia University, New York, New York 10027, United States.
Atomically precise clusters can be used to create single-electron devices wherein a single redox-active cluster is connected to two macroscopic electrodes via anchoring ligands. Unlike single-electron devices comprising nanocrystals, these cluster-based devices can be fabricated with atomic precision. This affords an unprecedented level of control over the device properties.
View Article and Find Full Text PDF