DFT; physisorption; selenium vacancy defect; thermodynamic stability; WSe2 monolayer; Ab initio molecular dynamics; Acceptor molecules; Density-functional-theory; Donor and acceptor; Electron-acceptor; Electron-donor molecules; Selenia vacancy defect; Tetracyanoquinodimethane; Vacancy Defects; Electronic, Optical and Magnetic Materials; Materials Chemistry; Electrochemistry
Abstract :
[en] Two-dimensional transition-metal dichalcogenide (2D-TMD) monolayers have recently attracted growing interest, thanks to their excellent optoelectronic properties, especially a moderate direct band gap in the visible spectral range and an extremely strong light-matter interaction. Herein, by means of density functional theory (DFT) and ab initio molecular dynamics (AIMD), we systematically investigate the chemical doping of the WSe2 monolayer upon non-covalent attachment of electron donor and acceptor molecules, namely, fullerenes (C20, C26, and C60), tetrathiafulvalene (TTF), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). Our results confirm that the physisorbed molecules stack on WSe2 via a weak van der Waals interaction; this precludes any significant damage in the basal-plane structure of the monolayer. In turn, the modifications in the carrier density in the WSe2 monolayer due to organic dopants result in a change of the work function by up to 0.41 eV. By performing AIMD calculations, we show that the effect is more pronounced upon increasing the coverage density of physisorbed TTF and TCNQ molecules. The impact of Se-vacancy (VSe) defects on the electronic properties of the WSe2 monolayer and thermodynamic stability of physisorption (including the molecular density) is also considered. Interestingly, the molecules demonstrate an ability to modulate the degree of spatial localization of VSe trap states. Moreover, the shift of the Fermi level upon molecular adsorption also enables further stabilization of charged defect states associated to a VSe vacancy. The pronounced effect of molecular adsorption on the VSe defect behavior in WSe2 might open the door for potential engineering of defect states in 2D TMDs.
Gali, Adam ; Wigner Research Centre for Physics, Budapest, Hungary ; Department of Atomic Physics, Budapest University of Technology and Economics, Budapest, Hungary
Cornil, Jérôme ; Université de Mons - UMONS > Faculté des Science > Service de Chimie des matériaux nouveaux
Pershin, Anton ; Wigner Research Centre for Physics, Budapest, Hungary ; Department of Atomic Physics, Budapest University of Technology and Economics, Budapest, Hungary
Language :
English
Title :
Non-covalent Functionalization of Pristine and Defective WSe2 by Electron Donor and Acceptor Molecules
R400 - Institut de Recherche en Science et Ingénierie des Matériaux R150 - Institut de Recherche sur les Systèmes Complexes
Funders :
Wallonie-Bruxelles International Nemzeti Kutat?si Fejleszt?si ?s Innov?ci?s Hivatal Horizon 2020 Framework Programme Fonds De La Recherche Scientifique - FNRS Quantum Information National Laboratory Region of Wallonie Ministry of Innovation and Technology of Hungary
Funding text :
This work was supported by the Belgian National Fund for Scientific Research (FRS-FNRS), Wallonie-Bruxelles International (WBI), and Region of Wallonie (RW) within the project of 2D Materials and FNRS-TOREADOR project. Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI) funded by F.R.S.-FNRS under grant 2.5020.11. A.M. acknowledges the financial support from EC through the H2020-DT-NMBP-11-2020 project GA no. 953167 (OpenModel). A.G. acknowledges the financial support from the National Research, Development and Innovation Office in Hungary (NKFIH) grant no. KKP129866 (National Excellence Program) as well as from the Quantum Information National Laboratory sponsored via the Ministry of Innovation and Technology of Hungary. J.C. is an FNRS research director. We also thank Dr. Arrigo Calzolari (CNR Researcher) for his fruitful comments.
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