Publications

Pentacene is an important model organic semiconductor in both the singlet exciton fission (SF) and organic electronics communities. We have investigated the effect of changing crystal structure on the SF process, generating multiple triplet excitons from an initial singlet exciton, and subsequent triplet recombination. Unlike for similar organic semiconductors that have strong SF sensitive to polymorphism, we find almost no quantitative difference between the kinetics of triplet pair (TT) formation in the two dominant polymorphs of pentacene. Both pairwise dimer coupling and momentum-space crystal models predict much faster TT formation from the bright singlet excited state of the Bulk vs ThinFilm polymorph, contrasting with the experiment. GW and Bethe-Salpeter equation calculations, including exciton-phonon coupling, reveal that ultrafast phonon-driven transitions in the ThinFilm polymorph compensate the intrinsically slower purely Coulomb-mediated TT formation channel, rationalizing the similarity in observed rates. Taking into account the influence of subtle structural distinctions on both the direct and phonon-mediated SF pathways reveals a predictive capability to these methods, expected to be applicable to a wide variety of molecular crystals.

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.

Heterostructures of layered transition metal dichalcogenides (TMDs) host long-lived, tunable excitons, making them intriguing candidates for material-based quantum information applications. Light absorption in these systems induces a plethora of optically excited states that hybridize both interlayer and intralayer characteristics, providing a distinctive starting point for their relaxation processes, in which the interplay between generated electron-hole pairs and their scattering with phonons play a key role. We present a first-principles theoretical approach to compute phonon-induced exciton decomposition due to rapid occupation of electron-hole pairs with finite momentum and opposite spin. Using the MoSe2/WSe2 heterostructure as a case study, we observe a reduction in the optical activity of bright states upon phonon scattering already in the first few femtoseconds after a photoexcitation, driving exciton interlayer delocalization and subsequent variations in the exciton spin. Our results reveal an unexpected and previously unexplored starting point for exciton relaxation dynamics, suggesting increased availability for coherent interactions and nonradiative processes through ultrafast changes in exciton momentum, spatial, and spin properties upon light excitation.

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 WS2graphene and MoS2graphene 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.

The presence of chalcogen vacancies in monolayer transition metal dichalcogenides (TMDs) leads to excitons with mixed localized-delocalized character and to reduced valley selectivity. Recent experimental advances in defect design in TMDs allow for a close examination of such mixed exciton states as a function of their degree of circular polarization under external magnetic fields, revealing strongly varying defect-induced magnetic properties. A theoretical understanding of these observations and their physical origins demands a predictive, structure-sensitive theory. In this work, we study the effect of chalcogen vacancies on the exciton magnetic properties in monolayer MoS2. Using many-body perturbation theory, we show how the complex excitonic picture associated with the presence of defectswith reduced valley and spin selectivity due to hybridized electron-hole transitionsleads to a structurally controllable exciton magnetic response. We find a variety of g-factors with changing magnitudes and sign depending on the exciton energy and character. Our findings suggest a pathway to tune the nature of the excitonsand by that their magneto-optical propertiesthrough
defect architecture.

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.

2D-semiconductors with strong lightmatter 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.

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.

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.

Two-dimensional (2D) excitons arise from electron-hole confinement along one spatial dimension. Such excitations are often described in terms of Frenkel or Wannier models according to the degree of exciton spatial localization and the surrounding dielectric environment. In hybrid material systems, such as the 2D perovskites, the two models break down at the intermediate regime where a different physical description is needed. We significantly enrich this framework of studies by considering a tunable airstable material platform where covalently bonded metalchalcogenide layers are spaced by organic ligands that provide confinement barriers for charge carriers in the inorganic layer. As representative of the material class, we consider self-assembled,layered bulk silver benzeneselenolate, [AgSePh]∞. We show that in this non-polar dielectric environment, strongly anisotropic excitons dominate the optical transitions. We then investigate the charge carriers transport, critical aspect for most optoelectronic devices, in a [AgSePh]∞ nanocrystal (NC) film. UV photoemission spectroscopy is used to extract the valence band energy edge and suitable metal contacts were fabricated to inject charge carriers. By temperature-dependent electrical measurements the activation energy for dark charge transport was in was determined to be 1.10eV. Photo-generated carriers could be extracted and the wavelength-dependent photo-response of the NC film suggest possible use of this materials as UV photodetector. We therefore built a planar photo-detector and characterized it in terms of sensitivity and frequency-dependent response. Finally, given the versatility of the [AgSePh]∞ NC film we validated its reliability as air-stable UV detector on flexible substrates.

In emerging photovoltaic and photocatalytic systems, correlated electron-hole excitations called excitons often serve as carriers in energy transfer processes. Structural complexities, such as reduced dimensionalities, interface compositions, and the presence of impurities, are closely coupled to exciton properties and decay processes. In this talk, I will describe a computational approach to study the excitonic phenomena in materials of complex structures, using ab initio many-body perturbation theory. I will specifically discuss many-body effects on optical and exciton phenomena in and between layered transition metal dichalcogenides, where a mixed nature of electron-hole interactions control the optical signatures and structurally-tunable selection rules. I will further present a new approach to study exciton decay processes in such functional materials from first principles, employing a rate-equation perturbative scheme to exciton-exciton and exciton-phonon interactions.

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 WS2 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.

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.

We measure the conductance of unmodified peptides at the single-molecule level using the scanning tunneling microscope-based break-junction method, utilizing the N-terminal amine group and the C-terminal carboxyl group as gold metal-binding linkers. Our conductance measurements of oligoglycine and oligoalanine backbones do not rely on peptide side-chain linkers. We compare our results with alkanes terminated asymmetrically with an amine group on one end and a carboxyl group on the other to show that peptide bonds decrease the conductance of an otherwise saturated carbon chain. Using a newly developed first-principles approach, we attribute the decrease in conductance to charge localization at the peptide bond, which reduces the energy of the frontier orbitals relative to the Fermi energy and the electronic coupling to the leads, lowering the tunneling probability. Crucially, this manifests as an increase in conductance decay of peptide backbones with increasing length when compared with alkanes.

The energy positions of frontier orbitals in organic electronic materials are often studied experimentally by (inverse) photoemission spectroscopy and theoretically within density functional theory. However, standard exchange-correlation functionals often result in too small fundamental gaps, may lead to wrong orbital energy ordering, and do not capture polarization-induced gap renormalization. Here we examine these issues and a strategy for overcoming them by studying the gas phase and bulk electronic structure of the organic molecule quinacridone (5Q), a promising material with many interesting properties for organic devices. Experimentally we perform angle-resolved photoemission spectroscopy (ARUPS) on thin films of the crystalline β phase of 5Q. Theoretically we employ an optimally tuned range-separated hybrid functional (OT-RSH) within density functional theory. For the gas phase molecule, our OT-RSH result for the ionization potential (IP) represents a substantial improvement over the semilocal PBE and the PBE0 hybrid functional results, producing an IP in quantitative agreement with experiment. For the bulk crystal we take into account the correct screening in the bulk, using the recently developed optimally tuned screened range-separated hybrid (OT-SRSH) approach, while retaining the optimally tuned parameters for the range separation and the short-range Fock exchange. This leads to a band gap narrowing due to polarization effects and results in a valence band spectrum in excellent agreement with experimental ARUPS data, with respect to both peak positions and heights. Finally, full-frequency G0W0 results based on a hybrid functional starting point are shown to agree with the OT-SRSH approach, improving substantially on the PBE-starting point.