Range-Separated Hybrid Functionals for Mixed-Dimensional Heterojunctions: Application to Phthalocyanines/MoS2

Abstract

We analyze the electronic structure and level alignment of transition-metal phthalocyanine (MPc) molecules adsorbed on two-dimensional MoS${}_2$ employing density functional theory (DFT) calculations. We develop a procedure for multi-objective optimal tuning of parameters of range-separated hybrid functionals in these mixed-dimensional systems. Using this procedure, which leads to the asymptotically-correct exchange-correlation potential between molecule and two-dimensional material, we obtain electronic structures consistent with experimental photoemission results for both energy level alignment and electronic bandgaps, representing a significant advance compared to standard DFT methods. We elucidate the MoS${}_2$ valence resonance with the transition-metal phthalocyanine non-frontier 3$d$ orbitals and its dependence on the transition metal atomic number. Based on our calculations, we derive parameter-free, model self-energy corrections that quantitatively accounts for the effects of the heterogeneous dielectric environment on the electronic structure of these mixed-dimensional heterojunctions.

References in corpus (22)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Advanced capabilities for materials modelling with Quantum ESPRESSO
• Optimized norm-conserving Vanderbilt pseudopotentials
• Emerging Device Applications for Semiconducting Two-Dimensional Transition Metal Dichalcogenides
• The PseudoDojo: Training and grading a 85 element optimized norm-conserving pseudopotential table
• Optical Spectrum of MoS${}_2$: Many-body Effects and Diversity of Exciton States
• Mixed-Dimensional van der Waals Heterostructures
• Theory of Neutral and Charged Excitons in Monolayer Transition Metal Dichalcogenides
• Quasiparticle band structures and optical properties of strained monolayer MoS2 and WS2
• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• Fundamental gaps of finite systems from the eigenvalues of a generalized Kohn-Sham method
• Screening and Many-Body Effects in Two-Dimensional Crystals: Monolayer MoS${}_2$
• Hybrid, Gate-Tunable, van der Waals p-n Heterojunctions from Pentacene and MoS2
• The dielectric genome of van der Waals heterostructures
• A Data Ecosystem to Support Machine Learning in Materials Science
• Environmentally-Sensitive Theory of Electronic and Optical Transitions in Atomically-Thin Semiconductors
• Large-area, low-voltage, anti-ambipolar heterojunctions from solution-processed semiconductors
• Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
• Quantitative Current-Voltage Characteristics in Molecular Junctions from First Principles
• Self-Aligned van der Waals Heterojunction Diodes and Transistors
• Dielectric dependent hybrid functionals for heterogeneous materials
• Dielectric Screening by 2D Substrates

Cited by in corpus (4)

• Transferable screened range-separated hybrid functionals for electronic and optical properties of van der Waals materials
• Quasiparticle electronic structure of phthalocyanine:TMD interfaces from first-principles $GW$
• Density functional descriptions of interfacial electronic structure
• Collective Electrostatics and Band Alignment in Janus MoSTe nanotubes