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ACS Nano. 2014 Jan 28;8(1):430-42. doi: 10.1021/nn406024m. Epub 2013 Dec 11.

Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template.

ACS nano

Sushobhan Joshi, Felix Bischoff, Ralph Koitz, David Ecija, Knud Seufert, Ari Paavo Seitsonen, Jürg Hutter, Katharina Diller, José I Urgel, Hermann Sachdev, Johannes V Barth, Willi Auwärter

Affiliations

  1. Physik Department E20, Technische Universität München , James Franck Strasse 1, D-85748 Garching, Germany.

PMID: 24328081 DOI: 10.1021/nn406024m

Abstract

Suitable templates to steer the formation of nanostructure arrays on surfaces are indispensable in nanoscience. Recently, atomically thin sp(2)-bonded layers such as graphene or boron nitride (BN) grown on metal supports have attracted considerable interest due to their potential geometric corrugation guiding the positioning of atoms, metallic clusters or molecules. Here, we demonstrate three specific functions of a geometrically smooth, but electronically corrugated, sp(2)/metal interface, namely, BN/Cu(111), qualifying it as a unique nanoscale template. As functional adsorbates we employed free-base porphine (2H-P), a prototype tetrapyrrole compound, and tetracyanoquinodimethane (TCNQ), a well-known electron acceptor. (i) The electronic moirons of the BN/Cu(111) interface trap both 2H-P and TCNQ, steering self-organized growth of arrays with extended molecular assemblies. (ii) We report an effective decoupling of the trapped molecules from the underlying metal support by the BN, which allows for a direct visualization of frontier orbitals by scanning tunneling microscopy (STM). (iii) The lateral molecular positioning in the superstructured surface determines the energetic level alignment; i.e., the energy of the frontier orbitals, and the electronic gap are tunable.

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