Donors, Acceptors and a Bit of Aromatics: Electronic Interactions of Molecular Adsorbates on hBN and MoS2 Monolayers
Authors/Creators
- 1. Department of Chemistry, Universität Zürich, 8057 Zürich, Switzerland. Pritzker School of Molecular Engineering, University of Chicago, 60637, Chicago, USA
- 2. Physics Department and IRIS Adlesrshof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany. Department of Physics, Free University Berlin, 14195 Berlin, Germany
- 3. Institute of Physics, Carl-von-Ossietzy Universität Oldenburg, 26129 Oldenburg, Germany
- 4. Physics Department and IRIS Adlesrshof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany
- 5. Physics Department and IRIS Adlesrshof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany. Institute of Physics, Carl-von-Ossietzy Universität Oldenburg, 26129 Oldenburg, Germany
- 6. Department of Chemistry, Universität Zürich, 8057 Zürich, Switzerland
Contributors
Contact person (2):
Project leader (2):
Project member (2):
- 1. Department of Chemistry, Universität Zürich, 8057 Zürich, Switzerland. Pritzker School of Molecular Engineering, University of Chicago, 60637, Chicago, USA
- 2. Physics Department and IRIS Adlesrshof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany. Department of Physics, Free University Berlin, 14195 Berlin, Germany
- 3. Institute of Physics, Carl-von-Ossietzy Universität Oldenburg, 26129 Oldenburg, Germany
- 4. Physics Department and IRIS Adlesrshof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany
- 5. Physics Department and IRIS Adlesrshof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany. Institute of Physics, Carl-von-Ossietzy Universität Oldenburg, 26129 Oldenburg, Germany
- 6. Department of Chemistry, Universität Zürich, 8057 Zürich, Switzerland
Description
The design of low-dimensional organic-inorganic hybrid interfaces for the next generation of optoelectronic applications requires an in-depth understanding of the microscopic mechanisms ruling the electronic interactions in these systems. In this work, we present a first-principles study based on density-functional theory inspecting the structural, energetic, and electronic properties of five molecular donors and acceptors adsorbed on freestanding hexagonal boron nitride (hBN) and molibdenum disulfide (MoS2) monolayers. All considered heterostructures are stable, due to the crucial contribution of dispersion interactions, which are maximed by the overall flat arrangement of the physisorbed molecules on both substrates. The level alignment of the hybrid systems depends on the characteristics of the constituents. On hBN, both type-I and type-II heterostructures may form, depending on the relative energies of the frontier orbitals with respect to the vacuum level. On the other hand, all MoS2-based hybrid systems exhibit a type-II level alignment, with the molecular frontier orbitals positioned across the energy gap of the semiconductor. The electronic structure of the hybrid materials is further determined by the formation of interfacial dipole moments and by the wave-function hybridization between the organic and inorganic constituents. These results provide important indications for the design of novel low-dimensional hybrid materials with suitable characteristics for optoelectronics.