Tunable electronic energy level alignment and exciton diversity in organic-inorganic van der Waals heterostructures

Abstract

van der Waals stacking of two-dimensional (2D) materials offers a powerful platform for engineering material interfaces with tailored electronic and optical properties. While most van der Waals multilayers have featured inorganic monolayers, incorporating molecular monolayers introduces new degrees of tunability and functionality. Here, we investigate hybrid bilayers composed of atomically thin perylene-based molecular crystals interfaced with monolayer transition metal dichalcogenides (TMDs), specifically MoS2 and WS2. Using ab initio many-body perturbation theory within the GW approximation and the Bethe-Salpeter equation approach, we predict emergent properties beyond those of the isolated constituent systems. Notably, we find substantial renormalization of monolayer molecular crystal band gap due to TMD-induced polarization. Furthermore, by varying the TMD monolayer, we demonstrate tuning of the energy level alignment of the bilayer and subsequent control over a diversity of lowest-energy excitons, which include strongly bound hybrid excitons and long-lived charge-transfer excitons. These findings establish organic-inorganic van der Waals heterostructures as a promising class of materials for tunable optoelectronic devices and quantum excitonic phenomena, expanding the design space for low-dimensional systems.

23 pages, 5 figures

References in corpus (31)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Advanced capabilities for materials modelling with Quantum ESPRESSO
• 2D materials and van der Waals heterostructures
• Coupled spin and valley physics in monolayers of MoS2 and other group-VI dichalcogenides
• Optimized norm-conserving Vanderbilt pseudopotentials
• Atomically thin p-n junctions with van der Waals heterointerfaces
• Optical Spectrum of MoS${}_2$: Many-body Effects and Diversity of Exciton States
• Optimization Algorithm for the Generation of ONCV Pseudopotentials
• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• Evidence of high-temperature exciton condensation in 2D atomic double layers
• High-temperature superfluidity with indirect excitons in van der Waals heterostructures
• Screening and Many-Body Effects in Two-Dimensional Crystals: Monolayer MoS${}_2$
• Interlayer excitons and Band Alignment in MoS${}_2$/hBN/WSe${}_2$ van der Waals Heterostructures
• Quasiparticle and Optical Spectroscopy of Organic Semiconductors Pentacene and PTCDA from First Principles
• Coulomb-hole summations and energies for GW calculations with limited number of empty orbitals: a modified static remainder approach
• Defect-induced modification of low-lying excitons and valley selectivity in monolayer transition metal dichalcogenides
• Excitonic condensation in a symmetric electron-hole bilayer
• Exciton Liquid in Coupled Quantum Wells
• The impact of exciton delocalization on exciton-vibration interactions in organic semiconductors
• Accelerating $GW$-Based Energy Level Alignment Calculations for Molecule-Metal Interfaces Using a Substrate Screening Approach
• Heterobilayers of 2D materials as a platform for excitonic superfluidity
• Phonon-induced localization of excitons in molecular crystals from first principles
• Conditions for electronic hybridization between transition-metal dichalcogenide monolayers and physisorbed carbon-conjugated molecules
• Quasiparticle electronic structure of phthalocyanine:TMD interfaces from first-principles $GW$
• Tunable magneto-optical properties in MoS${}_2$ via defect-induced exciton transitions
• Exciton Fission Enhanced Silicon Solar Cell
• Dielectric screening at TMD:hBN interfaces: Monolayer-to-bulk transition, local-field effect, and spatial dependence
• Hybrid Frenkel-Wannier excitons facilitate ultrafast energy transfer at a 2D-organic interface
• Anisotropy of the Optical Properties of Pentacene:Black Phosphorus Interfaces
• Tunable electronic energy level alignment and exciton diversity in organic-inorganic van der Waals heterostructures

Cited by in corpus (1)

• Tunable electronic energy level alignment and exciton diversity in organic-inorganic van der Waals heterostructures