Absorption onset; Aromatic monomers; Charge transport mechanisms; Degree of conjugations; Diazonium chemistry; Extended conjugation; Molecular junction; Structural motifs; Physics and Astronomy (all); Physical and Theoretical Chemistry; General Physics and Astronomy
Abstract :
[en] This paper shows that molecular layers grown using diazonium chemistry on carbon surfaces have properties indicative of the presence of a variety of structural motifs. Molecular layers grown with aromatic monomers with thickness between 1 and ∼15 nm display optical absorption spectra with significant broadening but no change in band gap or onsets of absorption as a function of layer thickness. This suggests that there is no extended conjugation in these layers, contrary to the conclusions of previous work. Density-functional theory modelling of the non-conjugated versions of the constituent aromatic monomers reveals that the experimental trends in optical spectra can be recovered, thereby establishing limits to the degree of conjugation and the nature of the order of as-grown molecular layers. We conclude that the absence of both shifts in band gap and changes in absorption onset is a consequence of resonant conjugation within the layers being less than 1.5 monomer units, and that film disorder is the main origin of the optical spectra. These findings have important implications for understanding charge transport mechanisms in molecular junction devices, as the layers cannot be expected to behave as ideal, resonantly conjugated films, but should be viewed as a collection of mixed nonresonantly- and resonantly-conjugated monomers.
Disciplines :
Chemistry
Author, co-author :
Van Dyck, Colin ; Université de Mons - UMONS > Faculté des Sciences > Service Chimie Physique Théorique
Bergren, Adam Johan ; Nanotechnology Research Centre, National Research Council of Canada, 11427 Saskatchewan Drive, Edmonton, Alberta T6G 2M9, Canada. Adam.Bergren@nrc.ca
Mukundan, Vineetha ; Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada
Fereiro, Jerry A ; Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada
DiLabio, Gino A ; Department of Chemistry, The University of British Columbia, 3247 University Way, Kelowna, British Columbia V1V 1V7, Canada. Gino.DiLabio@ubc.ca and Faculty of Management, The University of British Columbia, 1137 Alumni Ave, Kelowna, British Columbia V1V 1V7, Canada
Language :
English
Title :
Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling.
Natural Sciences and Engineering Research Council of Canada Canada Foundation for Innovation British Columbia Knowledge Development Fund University of British Columbia Compute Canada
Funding text :
GAD thanks the National Sciences and Engineering Research Council, the Canadian Foundation for Innovation, the British Columbia Knowledge Development Fund, The University of British Columbia, and Compute Canada for their support of this work. CVD thanks the Laboratory for Chemistry of Novel Materials at the Universitéde Mons in Belgium for access to their computing facilities. We are very grateful to Professor Richard McCreery for providing resources to collect data and insightful discussions.
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