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Issue 36, 2018
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Molecular signature of polyoxometalates in electron transport of silicon-based molecular junctions

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Abstract

Polyoxometalates (POMs) are unconventional electro-active molecules with a great potential for applications in molecular memories, providing efficient processing steps onto electrodes are available. The synthesis of the organic–inorganic polyoxometalate hybrids [PM11O39{Sn(C6H4)C[triple bond, length as m-dash]C(C6H4)N2}]3− (M = Mo, W) endowed with a remote diazonium function is reported together with their covalent immobilization onto hydrogenated n-Si(100) substrates. Electron transport measurements through the resulting densely-packed monolayers contacted with a mercury drop as a top electrode confirms their homogeneity. Adjustment of the current–voltage curves with the Simmon's equation gives a mean tunnel energy barrier ΦPOM of 1.8 eV and 1.6 eV, for the Silicon–Molecules–Metal (SMM) junctions based on the polyoxotungstates (M = W) and polyoxomolybdates (M = Mo), respectively. This follows the trend observed in the electrochemical properties of POMs in solution, the polyoxomolybdates being easier to reduce than the polyoxotungstates, in agreement with lowest unoccupied molecular orbitals (LUMOs) of lower energy. The molecular signature of the POMs is thus clearly identifiable in the solid-state electrical properties and the unmatched diversity of POM molecular and electronic structures should offer a great modularity.

Graphical abstract: Molecular signature of polyoxometalates in electron transport of silicon-based molecular junctions

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Publication details

The article was received on 18 Jun 2018, accepted on 29 Aug 2018 and first published on 30 Aug 2018


Article type: Paper
DOI: 10.1039/C8NR04946G
Nanoscale, 2018,10, 17156-17165

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    Molecular signature of polyoxometalates in electron transport of silicon-based molecular junctions

    M. Laurans, K. Dalla Francesca, F. Volatron, G. Izzet, D. Guerin, D. Vuillaume, S. Lenfant and A. Proust, Nanoscale, 2018, 10, 17156
    DOI: 10.1039/C8NR04946G

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