Phonon-Driven Femtosecond Dynamics of Excitons in Crystalline Pentacene from First Principles.

Nonradiative exciton relaxation processes are critical for energy transduction and transport in optoelectronic materials, but how these processes are connected to the underlying crystal structure and the associated electron, exciton, and phonon band structures, as well as the interactions of all these particles, is challenging to understand. Here, we present a first-principles study of exciton-phonon relaxation pathways in pentacene, a paradigmatic molecular crystal and optoelectronic semiconductor. We compute the momentum- and band-resolved exciton-phonon interactions, and use them to analyze key scattering channels. We find that both exciton intraband scattering and interband scattering to parity-forbidden dark states occur on the same ∼100 fs timescale as a direct consequence of the longitudinal-transverse splitting of the bright exciton band. Consequently, exciton-phonon scattering exists as a dominant nonradiative relaxation channel in pentacene. We further show how the propagation of an exciton wave packet is connected with crystal anisotropy, which gives rise to the longitudinal-transverse exciton splitting and concomitant anisotropic exciton and phonon dispersions. Our results provide a framework for understanding the role of exciton-phonon interactions in exciton nonradiative lifetimes in molecular crystals and beyond.

Photovoltage and Photocurrent Absorption Spectra of Sulfur Vacancies Locally Patterned in Monolayer MoS2.

We report on the optical absorption characteristics of selectively positioned sulfur vacancies in monolayer MoS2, as observed by photovoltage and photocurrent experiments in an atomistic vertical tunneling circuit at cryogenic and room temperature. Charge carriers are resonantly photoexcited within the defect states before they tunnel through an hBN tunneling barrier to a graphene-based drain contact. Both photovoltage and photocurrent characteristics confirm the optical absorption spectrum as derived from ab initio GW and Bethe-Salpeter equation approximations. Our results reveal the potential of single-vacancy tunneling devices as atomic-scale photodiodes.

Reduced Absorption Due to Defect-Localized Interlayer Excitons in Transition-Metal Dichalcogenide-Graphene Heterostructures.

Associating atomic vacancies to excited-state transport phenomena in two-dimensional semiconductors demands a detailed understanding of the exciton transitions involved. We study the effect of such defects on the electronic and optical properties of WS2-graphene and MoS2-graphene van der Waals heterobilayers, employing many-body perturbation theory. We find that chalcogen defects and the graphene interface radically alter the optical properties of the transition-metal dichalcogenide in the heterobilayer, due to a combination of dielectric screening and the many-body nature of defect-induced intralayer and interlayer optical transitions. By analyzing the intrinsic radiative rates of the subgap excitonic features, we show that while defects introduce low-lying optical transitions, resulting in excitons with non-negligible oscillator strength, they decrease the optical response of the pristine-like transition-metal dichalcogenide intralayer excitons. Our findings relate excitonic features with interface design for defect engineering in photovoltaic and transport applications.

Optical absorption of interlayer excitons in transition-metal dichalcogenide heterostructures.

Interlayer excitons, electron-hole pairs bound across two monolayer van der Waals semiconductors, offer promising electrical tunability and localizability. Because such excitons display weak electron-hole overlap, most studies have examined only the lowest-energy excitons through photoluminescence. We directly measured the dielectric response of interlayer excitons, which we accessed using their static electric dipole moment. We thereby determined an intrinsic radiative lifetime of 0.40 nanoseconds for the lowest direct-gap interlayer exciton in a tungsten diselenide/molybdenum diselenide heterostructure. We found that differences in electric field and twist angle induced trends in exciton transition strengths and energies, which could be related to wave function overlap, moiré confinement, and atomic reconstruction. Through comparison with photoluminescence spectra, this study identifies a momentum-indirect emission mechanism. Characterization of the absorption is key for applications relying on light-matter interactions.

Bright excitonic multiplexing mediated by dark exciton transition in two-dimensional TMDCs at room temperature.

2D-semiconductors with strong light-matter interaction are attractive materials for integrated and tunable optical devices. Here, we demonstrate room-temperature wavelength multiplexing of the two-primary bright excitonic channels (Ab-, Bb-) in monolayer transition metal dichalcogenides (TMDs) arising from a dark exciton mediated transition. We present how tuning dark excitons via an out-of-plane electric field cedes the system equilibrium from one excitonic channel to the other, encoding the field polarization into wavelength information. In addition, we demonstrate how such exciton multiplexing is dictated by thermal-scattering by performing temperature dependent photoluminescence measurements. Finally, we demonstrate experimentally and theoretically how excitonic mixing can explain preferable decay through dark states in MoX2 in comparison with WX2 monolayers. Such field polarization-based manipulation of excitonic transitions can pave the way for novel photonic device architectures.

Theory of Chirality Induced Spin Selectivity: Progress and Challenges.

A critical overview of the theory of the chirality-induced spin selectivity (CISS) effect, that is, phenomena in which the chirality of molecular species imparts significant spin selectivity to various electron processes, is provided. Based on discussions in a recently held workshop, and further work published since, the status of CISS effects-in electron transmission, electron transport, and chemical reactions-is reviewed. For each, a detailed discussion of the state-of-the-art in theoretical understanding is provided and remaining challenges and research opportunities are identified.

Identifying Hidden Intracell Symmetries in Molecular Crystals and Their Impact for Multiexciton Generation.

Organic molecular crystals are appealing for next-generation optoelectronic applications due to their multiexciton generation processes that can increase the efficiency of photovoltaic devices. However, a general understanding of how crystal structures affect these processes is lacking, requiring computationally demanding calculations for each material. Here we present an approach to understand and classify organic crystals and elucidate multiexciton processes. We show that organic crystals that are composed of two sublattices are well-approximated by effective fictitious systems of higher translational symmetry. Within this framework, we derive hidden selection rules in crystal pentacene and predict that the bulk polymorph supports fast Coulomb-mediated singlet fission with a transition rate about 2 orders of magnitude faster than that of the thin-film polymorph, a result confirmed with many-body perturbation theory calculations. Our approach is based on density-functional theory calculations and provides design principles for the experimental and computational discovery of new materials with tailored excitonic properties.

Anisotropic 2D excitons unveiled in organic-inorganic quantum wells.

Two-dimensional (2D) excitons arise from electron-hole confinement along one spatial dimension. Such excitations are often described in terms of Frenkel or Wannier limits according to the degree of exciton spatial localization and the surrounding dielectric environment. In hybrid material systems, such as the 2D perovskites, the complex underlying interactions lead to excitons of an intermediate nature, whose description lies somewhere between the two limits, and a better physical description is needed. Here, we explore the photophysics of a tuneable materials platform where covalently bonded metal-chalcogenide layers are spaced by organic ligands that provide confinement barriers for charge carriers in the inorganic layer. We consider self-assembled, layered bulk silver benzeneselenolate, [AgSePh]∞, and use a combination of transient absorption spectroscopy and ab initio GW plus Bethe-Salpeter equation calculations. We demonstrate that in this non-polar dielectric environment, strongly anisotropic excitons dominate the optical transitions of [AgSePh]∞. We find that the transient absorption measurements at room temperature can be understood in terms of low-lying excitons confined to the AgSe planes with in-plane anisotropy, featuring anisotropic absorption and emission. Finally, we present a pathway to control the exciton behaviour by changing the chalcogen in the material lattice. Our studies unveil unexpected excitonic anisotropies in an unexplored class of tuneable, yet air-stable, hybrid quantum wells, offering design principles for the engineering of an ordered, yet complex dielectric environment and its effect on the excitonic phenomena in such emerging materials.

Exciton Modulation in Perylene-Based Molecular Crystals Upon Formation of a Metal-Organic Interface From Many-Body Perturbation Theory.

Excited-state processes at organic-inorganic interfaces consisting of molecular crystals are essential in energy conversion applications. While advances in experimental methods allow direct observation and detection of exciton transfer across such junctions, a detailed understanding of the underlying excitonic properties due to crystal packing and interface structure is still largely lacking. In this work, we use many-body perturbation theory to study structure-property relations of excitons in molecular crystals upon adsorption on a gold surface. We explore the case of the experimentally-studied octyl perylene diimide (C8-PDI) as a prototypical system, and use the GW and Bethe-Salpeter equation (BSE) approach to quantify the change in quasiparticle and exciton properties due to intermolecular and substrate screening. Our findings provide a close inspection of both local and environmental structural effects dominating the excitation energies and the exciton binding and nature, as well as their modulation upon the metal-organic interface composition.

Signatures of Dimensionality and Symmetry in Exciton Band Structure: Consequences for Exciton Dynamics and Transport.

Exciton dynamics, lifetimes, and scattering are directly related to the exciton dispersion or band structure. Here, we present a general theory for exciton band structure within both ab initio and model Hamiltonian approaches. We show that contrary to common assumption, the exciton band structure contains nonanalytical discontinuities-a feature which is impossible to obtain from the electronic band structure alone. These discontinuities are purely quantum phenomena, arising from the exchange scattering of electron-hole pairs. We show that the degree of these discontinuities depends on materials' symmetry and dimensionality, with jump discontinuities occurring in 3D and different orders of removable discontinuities in 2D and 1D, whose details depend on the exciton degeneracy and material thickness. We connect these features to the early stages of exciton dynamics, radiative lifetimes, and diffusion constants, in good correspondence with recent experimental observations, revealing that the discontinuities in the band structure lead to ultrafast ballistic transport and suggesting that measured exciton diffusion and dynamics are influenced by the underlying exciton dispersion.

The role of chalcogen vacancies for atomic defect emission in MoS2.

For two-dimensional (2D) layered semiconductors, control over atomic defects and understanding of their electronic and optical functionality represent major challenges towards developing a mature semiconductor technology using such materials. Here, we correlate generation, optical spectroscopy, atomic resolution imaging, and ab initio theory of chalcogen vacancies in monolayer MoS2. Chalcogen vacancies are selectively generated by in-vacuo annealing, but also focused ion beam exposure. The defect generation rate, atomic imaging and the optical signatures support this claim. We discriminate the narrow linewidth photoluminescence signatures of vacancies, resulting predominantly from localized defect orbitals, from broad luminescence features in the same spectral range, resulting from adsorbates. Vacancies can be patterned with a precision below 10 nm by ion beams, show single photon emission, and open the possibility for advanced defect engineering of 2D semiconductors at the ultimate scale.

Rational Passivation of Sulfur Vacancy Defects in Two-Dimensional Transition Metal Dichalcogenides.

Structural defects vary the optoelectronic properties of monolayer transition metal dichalcogenides, leading to concerted efforts to control defect type and density via materials growth or postgrowth passivation. Here, we explore a simple chemical treatment that allows on-off switching of low-lying, defect-localized exciton states, leading to tunable emission properties. Using steady-state and ultrafast optical spectroscopy, supported by ab initio calculations, we show that passivation of sulfur vacancy defects, which act as exciton traps in monolayer MoS2 and WS2, allows for controllable and improved mobilities and an increase in photoluminescence up to 275-fold, more than twice the value achieved by other chemical treatments. Our findings suggest a route for simple and rational defect engineering strategies for tunable and switchable electronic and excitonic properties through passivation.

Quantum Phase Transitions of Trilayer Excitons in Atomically Thin Heterostructures.

We determine the phase diagram of excitons in a symmetric transition-metal dichalcogenide 3-layer heterostructure. First principles calculations reveal interlayer exciton states of a symmetric quadrupole, from which higher energy asymmetric dipole states are composed. We find quantum phase transitions between a repulsive quadrupolar and an attractive staggered dipolar lattice phases, driven by a competition between interactions and single exciton energies. The different internal quantum state of excitons in each phase is a striking example of a system where single-particle and interacting many-body states are coupled.

Large Spin-Orbit Splitting of Deep In-Gap Defect States of Engineered Sulfur Vacancies in Monolayer WS_{2}.

Structural defects in 2D materials offer an effective way to engineer new material functionalities beyond conventional doping. We report on the direct experimental correlation of the atomic and electronic structure of a sulfur vacancy in monolayer WS_{2} by a combination of CO-tip noncontact atomic force microscopy and scanning tunneling microscopy. Sulfur vacancies, which are absent in as-grown samples, were deliberately created by annealing in vacuum. Two energetically narrow unoccupied defect states followed by vibronic sidebands provide a unique fingerprint of this defect. Direct imaging of the defect orbitals, together with ab initio GW calculations, reveal that the large splitting of 252±4 meV between these defect states is induced by spin-orbit coupling.

How Substitutional Point Defects in Two-Dimensional WS2 Induce Charge Localization, Spin-Orbit Splitting, and Strain.

Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS2) grown by chemical vapor deposition using scanning tunneling microscopy/spectroscopy, CO-tip noncontact atomic force microscopy, Kelvin probe force spectroscopy, density functional theory, and tight-binding calculations. We observe four different substitutional defects: chromium (CrW) and molybdenum (MoW) at a tungsten site, oxygen at sulfur sites in both top and bottom layers (OS top/bottom), and two negatively charged defects (CD type I and CD type II). Their electronic fingerprints unambiguously corroborate the defect assignment and reveal the presence or absence of in-gap defect states. CrW forms three deep unoccupied defect states, two of which arise from spin-orbit splitting. The formation of such localized trap states for CrW differs from the MoW case and can be explained by their different d shell energetics and local strain, which we directly measured. Utilizing a tight-binding model the electronic spectra of the isolectronic substitutions OS and CrW are mimicked in the limit of a zero hopping term and infinite on-site energy at a S and W site, respectively. The abundant CDs are negatively charged, which leads to a significant band bending around the defect and a local increase of the contact potential difference. In addition, CD-rich domains larger than 100 nm are observed, causing a work function increase of 1.1 V. While most defects are electronically isolated, we also observed hybrid states formed between CrW dimers. The important role of charge localization, spin-orbit coupling, and strain for the formation of deep defect states observed at substitutional defects in WS2 as reported here will guide future efforts of targeted defect engineering and doping of TMDs.

Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides.

Chalcogen vacancies are generally considered to be the most common point defects in transition metal dichalcogenide (TMD) semiconductors because of their low formation energy in vacuum and their frequent observation in transmission electron microscopy studies. Consequently, unexpected optical, transport, and catalytic properties in 2D-TMDs have been attributed to in-gap states associated with chalcogen vacancies, even in the absence of direct experimental evidence. Here, we combine low-temperature non-contact atomic force microscopy, scanning tunneling microscopy and spectroscopy, and state-of-the-art ab initio density functional theory and GW calculations to determine both the atomic structure and electronic properties of an abundant chalcogen-site point defect common to MoSe2 and WS2 monolayers grown by molecular beam epitaxy and chemical vapor deposition, respectively. Surprisingly, we observe no in-gap states. Our results strongly suggest that the common chalcogen defects in the described 2D-TMD semiconductors, measured in vacuum environment after gentle annealing, are oxygen substitutional defects, rather than vacancies.

Defect-Induced Modification of Low-Lying Excitons and Valley Selectivity in Monolayer Transition Metal Dichalcogenides.

We study the effect of point-defect chalcogen vacancies on the optical properties of monolayer transition metal dichalcogenides using ab initio GW and Bethe-Salpeter equation calculations. We find that chalcogen vacancies introduce unoccupied in-gap states and occupied resonant defect states within the quasiparticle continuum of the valence band. These defect states give rise to a number of strongly bound defect excitons and hybridize with excitons of the pristine system, reducing the valley-selective circular dichroism. Our results suggest a pathway to tune spin-valley polarization and other optical properties through defect engineering.

Quantitative Prediction of Optical Absorption in Molecular Solids from an Optimally Tuned Screened Range-Separated Hybrid Functional.

We show that fundamental gaps and optical spectra of molecular solids can be predicted quantitatively and nonempirically within the framework of time-dependent density functional theory (TDDFT) using the recently developed optimally tuned screened range-separated hybrid (OT-SRSH) functional approach. In this scheme, the electronic structure of the gas-phase molecule is determined by optimal tuning of the range-separation parameter in a range-separated hybrid functional. Screening and polarization in the solid state are taken into account by adding long-range dielectric screening to the functional form, with the modified functional used to perform self-consistent periodic-boundary calculations for the crystalline solid. We provide a comprehensive benchmark for the accuracy of our approach by considering the X23 set of molecular solids and comparing results obtained from TDDFT with those obtained from many-body perturbation theory in the GW-BSE approximation. We additionally compare results obtained from dielectric screening computed within the random-phase approximation to those obtained from the computationally more efficient many-body dispersion approach and find that this influences the fundamental gap but has little effect on the optical spectra. Our approach is therefore robust and can be used for studies of molecular solids that are typically beyond the reach of computationally more intensive methods.

Electronic structure of dipeptides in the gas-phase and as an adsorbed monolayer.

Peptide-based molecular electronic devices are promising due to the large diversity and unique electronic properties of biomolecules. These electronic properties can change considerably with peptide structure, allowing diverse design possibilities. In this work, we explore the effect of the side-chain of the peptide on its electronic properties, by using both experimental and computational tools to detect the electronic energy levels of two model peptides. The peptides include 2Ala and 2Trp as well as their 3-mercaptopropionic acid linker which is used to form monolayers on an Au surface. Specifically, we compare experimental ultraviolet photoemission spectroscopy measurements with density functional theory based computational results. By analyzing differences in frontier energy levels and molecular orbitals between peptides in gas-phase and in a monolayer on gold, we find that the electronic properties of the peptide side-chain are maintained during binding of the peptide to the gold substrate. This indicates that the energy barrier for the peptide electron transport can be tuned by the amino acid compositions, which suggests a route for structural design of peptide-based electronic devices.