Franckeite as a naturally occurring van der Waals heterostructure

Abstract

The fabrication of van der Waals heterostructures, artificial materials assembled by individual stacking of 2D layers, is among the most promising directions in 2D materials research. Until now, the most widespread approach to stack 2D layers relies on deterministic placement methods, which are cumbersome and tend to suffer from poor control over the lattice orientations and the presence of unwanted interlayer adsorbates. Here, we present a different approach to fabricate ultrathin heterostructures by exfoliation of bulk franckeite which is a naturally occurring and air stable van der Waals heterostructure (composed of alternating SnS 2-like and PbS-like layers stacked on top of each other). Presenting both an attractive narrow bandgap (<0.7 eV) and p-type doping, we find that the material can be exfoliated both mechanically and chemically down to few-layer thicknesses. We present extensive theoretical and experimental characterizations of the material's electronic properties and crystal structure, and explore applications for near-infrared photodetectors ; A.C.-G. acknowledges financial support from the BBVA Foundation through the fellowship 'I Convocatoria de Ayudas Fundacion BBVA a Investigadores, Innovadores y Creadores Culturales' ('Semiconductores ultradelgados: hacia la optpelectronica flexible'), from the MINECO (Ramón y Cajal 2014 program, RYC-2014-01406), from the MICINN (MAT2014-58399-JIN) and from European Commission under the Graphene Flagship, contract CNECTICT-604391. E.M.P. acknowledges financial support from the European Research Council (MINT, ERC-StG-307609) and from the MINECO of Spain (CTQ2014-60541-P). E.G. gratefully acknowledges the AMAROUT II fellowship program for receiving a grant for transnational mobility (Marie Curie Action, FP7-PEOPLE- 2011-COFUND (291803)). A.J.M.-M., G.R.-B. and N.A. acknowledge the support of the MICCINN/MINECO (Spain) through the programmes MAT2014-57915-R, BES-2012-057346 and FIS2011-23488 and Comunidad de Madrid (Spain) through the programme S2013/MIT-3007 (MAD2D). J.O.I. and H.S.J.v.d.Z. acknowledge the support of the Dutch organization for Fundamental Research on Matter (FOM) and by the Ministry of Education, Culture, and Science (OCW). M.A.N. acknowledeges the support of the MICCINN/MINECO (Spain) through the programmes MAT2013-49893-EXP and MAT2014-59315-R. Authors M.A.N., A.J.M.-M. and A.C.-G. acknowledge the support from ALBA Synchrotron for the experiments performed at Circe beamline (BL24-CIRCE) at ALBA Synchrotron with the collaboration of ALBA staff (proposal ID 2015091399). W.S.P. acknowledges CAPES Foundation, Ministry of Education of Brazil, under grant BEX 9476/13-0. W.S.P. and J.J.P. acknowledge MICCINN/MINECO (Spain) for financial support under grant FIS2013-47328-C02-1; the European Union structural funds and the Comunidad de Madrid MAD2D-CM programme under grant nos. P2013/MIT-3007 and P2013/MIT-2850; the Generalitat Valenciana under grant no. PROMETEO/2012/011