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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Delocalization of dark and bright excitons in flat-band materials and the optical properties of V2O5

Abstract The simplest picture of excitons in materials with atomic-like localization of electrons is that of Frenkel excitons, where electrons and holes stay close together, which is associated with a large binding energy. Here, using the example of the layered oxide V 2 O 5 , we show how localized charge-transfer excitations combine to form excitons that also have a huge binding energy but, at the same time, a large electron-hole distance, and we explain this seemingly contradictory finding. The anisotropy of the exciton delocalization is determined by the local anisotropy of the structure, whereas the exciton extends orthogonally to the chains formed by the crystal structure. Moreover, we show that the bright exciton goes together with a dark exciton of even larger binding energy and more pronounced anisotropy. These findings are obtained by combining first principles many-body perturbation theory calculations, ellipsometry experiments, and tight binding modelling, leading to very good agreement and a consistent picture. Our explanation is general and can be extended to other materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

On wavelength-dependent exciton lifetime distributions in reconstituted CP29 antenna of the photosystem II and its site-directed mutants

To provide more insight on the excitonic structure and exciton lifetimes of the wild type (WT) CP29 complex of Photosystem II (PSII) we measured high-resolution (low temperature) absorption, emission, and hole burned spectra for the A2 and B3 mutants, which lack chlorophylls a612 and b614 (Chls), respectively. Experimental and modeling results obtained for the WT CP29 and A2/B3 mutants provide new insight on the mutation-induced changes at the molecular level and shed more light on energy transfer dynamics. Simulations of the A2 and B3 optical spectra, using the second-order non-Markovian theory, and comparison with improved fits of WT CP29 optical spectra, provide more insight on their excitonic structure, mutation induced changes, and frequency-dependent distributions of exciton lifetimes (T 1 ). A new Hamiltonian obtained for WT CP29 reveals that deletion of Chls a612 or b614 induces changes in the site-energies of all remaining Chls. Hamiltonians obtained for A2 and B3 mutants are discussed in the context of the energy landscape of chlorophylls, excitonic structure and the transfer kinetics. Our data suggest that the lowest exciton states in A2 and B3 mutants are contributed by a611(57%), a610(17%), a615(15%) and a615(58%), a611(20%), a612(15%) Chls, respectively, although other compositions of lowest energy states are also discussed. Lastly, we argue that the calculated exciton decay times are consistent with both the hole-burning and recent transient absorption measurements. Wavelength-dependent T 1 distributions offer more insight into the interpretation of kinetic traces commonly described by discrete exponentials in global analysis/global fitting of transient absorption experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Excitons: Energetics and spatiotemporal dynamics

The concept of an exciton as a quasiparticle that represents collective excited states was originally adapted from solid-state physics and has been successfully applied to molecular aggregates by relying on the well-established limits of the Wannier exciton and the Frenkel exciton. However, the study of excitons in more complex chemical systems and solid materials over the past two decades has made it clear that simple concepts based on Wannier or Frenkel excitons are not sufficient to describe detailed excitonic behavior, especially in nano-structured solid materials, multichromophoric macromolecules, and complex molecular aggregates. In addition, important effects such as vibronic coupling, the influence of charge-transfer (CT) components, spin-state interconversion, and electronic correlation, which had long been studied but not fully understood, have turned out to play a central role in many systems. This has motivated new experimental approaches and theoretical studies of increasing sophistication. This article provides an overview of works addressing these issues that were published for A Special Topic of the Journal of Chemical Physics on ``Excitons: Energetics and spatio-temporal dynamics" and discusses their implications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Atomistically resolved hot exciton relaxation dynamics in CdSe quantum dots: Experiment and theory

Semiconductor quantum dots (QDs) are well known to give rise to a quantum confined structure of excitons. Because of this quantum confinement, new physics of hot exciton relaxation dynamics arises. Decades of work using transient absorption (TA) spectroscopy have yielded initial simple observations, such as estimates of the cooling rate from single pump photon energy experiments. More detailed TA experiments employed variable pump photon energies to measure excitonic state-resolved transition rates. These TA measurements, usually the simplest form, have been employed to characterize QDs and their relaxation dynamics to this day. Yet, these TA measurements are fundamentally lacking in their ability to measure energy-resolved hot exciton cooling, which requires observation of the full cooling history through the real excitonic manifold. Here, we employ coherent multi-dimensional spectroscopy (CMDS) to perform an atomistically directed study of hot exciton cooling in CdSe QDs, revealing energy resolved relaxation dynamics. CMDS experiments are compared with simulations and prior TA measurements and simpler theories. Our findings reveal a hot exciton relaxation dynamics landscape. This relaxation dynamics landscape is a linear or sub-linear function of excess energy for different structures of QDs, with a strong size dependence. Our model simulations parameterized by the empirical pseudopotential model reproduces the experimental functional form and the dependence upon QD diameter and shell.

Atomistic simulations↗
DOE OSTI2025

Possible Spin-Triplet Excitonic Insulator in the Ultraquantum Limit of HfTe 5

More than 50 years ago, excitonic insulators formed by the pairing of electrons and holes due to Coulomb interactions were first predicted [A. N. Kozlov and L. A. Maksimov, Sov. J. Exp. Theor. Phys. 21, 790 (1965); L. V. Keldysh and Y. V. Kopaev, Sov. Phys. Solid State 6, 2219 (1965); D. Jérome, T. M. Rice, and W. Kohn, Phys. Rev. 158, 462 (1967)]. Since then, excitonic insulators have been observed in various classes of materials, including quantum Hall bilayers, graphite, transition metal chalcogenides, and more recently in moiré superlattices. In these excitonic insulators, an electron and a hole with the same spin bind together, and the resulting exciton is a spin singlet. Here, we report the experimental observation of a spin-triplet excitonic insulator in the ultra-quantum limit of a three-dimensional topological material HfTe 5 . We observe that the spin-polarized zeroth Landau bands dispersing along the field direction cross each other beyond a characteristic magnetic field in HfTe 5 , forming the one-dimensional Weyl mode. Transport measurements reveal the emergence of a gap of about 2⁢5⁢0 μ⁢eV when the field surpasses a critical threshold. By performing the material-specific modeling, we identify this gap as a consequence of a spin-triplet exciton formation, where electrons and holes with opposite spin form bound states, and the translational symmetry is preserved. The system reaches charge neutrality following the gap opening, as evidenced by the zero Hall conductivity over a wide magnetic field range (10–72 T). In conclusion, our finding of the spin-triplet excitonic insulator paves the way for studying novel spin transport including spin superfluidity, spin Josephson currents, and Coulomb drag of spin currents in analogy to the transport properties associated with the layer pseudospin in quantum Hall bilayers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Coupled valence carrier and core-exciton dynamics in WS 2 probed by few-femtosecond extreme ultraviolet transient absorption spectroscopy

Few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy, performed with optical 500-1000 nm supercontinuum and broadband XUV pulses (30-50 eV), simultaneously probes dynamics of photoexcited carriers in WS$_{2}$ at the W O$_3$ edge (37-45 eV) and carrier-induced modifications of core-exciton absorption at the W N$_{6,7}$ edge (32-37 eV). Access to continuous core-to-conduction band absorption features and discrete core-exciton transitions in the same XUV spectral region in a semiconductor provides a novel means to investigate the effect of carrier excitation on core-exciton dynamics. The core-level transient absorption spectra, measured with either pulse arriving first to explore both core-level and valence carrier dynamics, reveal that core-exciton transitions are strongly influenced by the photoexcited carriers. A $1.2\pm0.3$ ps hole-phonon relaxation time and a $3.1\pm0.4$ ps carrier recombination time are extracted from the XUV transient absorption spectra from the core-to-conduction band transitions at the W O$_{3}$ edge. Global fitting of the transient absorption signal at the W N$_{6,7}$ edge yields $\sim 10$ fs coherence lifetimes of core-exciton states and reveals that the photoexcited carriers, which alter the electronic screening and band filling, are the dominant contributor to the spectral modifications of core-excitons and direct field-induced changes play a minor role. This work provides a first look at the modulations of core-exciton states by photoexcited carriers and advances our understanding of carrier dynamics in metal dichalcogenides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Tunable magneto-optical properties in MoS 2 via defect-induced exciton transitions

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 MoS 2 . Using many-body perturbation theory, we show how the complex excitonic picture associated with the presence of defects—with reduced valley and spin selectivity due to hybridized electron-hole transitions—leads to a structurally controllable exciton magnetic response. We find a variety of $\textit{g}$-factors with changing magnitudes and sign depending on the exciton energy and character. Further, our findings suggest a pathway to tune the nature of the excitons—and by that their magneto-optical properties—through defect architecture.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

High-Temperature Observation of Intralayer, Interlayer, and Rydberg Excitons in Bulk Van Der Waals Alloy Single Crystals

Transition metal dichalcogenides exhibit remarkable optical properties due to the diverse number of strongly bound excitons, which can be fine-tuned by alloying. Despite a flurry of research activity in characterizing these excitons, a comprehensive and profound understanding of their behavior with temperature is lacking. Here, we report the rich spectrum of excitonic features within bulk van der Waals alloy Mo0.5 W0.5 S2 and Mo0.5 W0.5 Se2 single crystals through temperature-dependent reflectance spectroscopy and first-principles calculations. We observed Rydberg excitons and interlayer excitons in both the single crystals. Notably, we provide the first experimental evidence of highly energetic A' and B' excitons in Mo0.5 W0.5 S2 at room temperature. The strong carrier-phonon scattering significantly broadens the A', B', and interlayer excitons at room temperature in bulk Mo0.5 W0.5 S2 single crystal compared to its selenide. Our findings, supported by density functional theory and Bethe-Salpeter equation calculations, signify the crucial role of carrier-phonon interactions. These results open pathways for next-generation optoelectronic devices and quantum technologies operating at high temperature.

excitons↗
DOE OSTI2025

Polarization-resolved core exciton dynamics in LiF using attosecond transient absorption spectroscopy

The ability to control absorption by modifying the polarization of light presents an exciting opportunity to experimentally determine the orbital alignment of absorption features. Here, attosecond extreme ultraviolet (XUV) transient absorption spectroscopy is used to investigate the polarization dependence of core exciton dynamics in LiF thin films at the Li + K edge. XUV pulses excite electrons from the Li 1s core level into the conduction band, allowing for the formation of a p-orbital-like core exciton, aligned along the XUV light polarization axis. A sub-5 fs near-infrared (NIR) probe pulse then arrives at variable time delays, perturbing the XUV-excited states and allowing the coherence decay of the core exciton to be mapped. The coherence lifetimes are found to be ≈ 2.4 ± 0.4 fs, which is attributed to a phonon-mediated dephasing mechanism as in previous core exciton studies. The differential absorption features are also shown to be sensitive to the relative polarization of the XUV and NIR fields. The parallel NIR probe induces couplings between the initial XUV-excited p-like bright exciton and s-like dark excitons. When crossed pump and probe polarizations are used, the coupling between the bright and dark states is no longer dipole-allowed, and the transient absorption signal associated with the coupling is suppressed by approximately 90%. This interpretation is supported by simulations of a few-level model system, as well as analysis of the calculated band structure. Here, the results indicate that laser polarization can serve as a powerful experimental tool for exploring the orbital alignment of core excitonic states in solid-state materials.

Attosecond laser spectroscopy↗
DOE OSTI2022

Ultrafast Excitonic Response in Two-Dimensional Hybrid Perovskites Driven by Intense Midinfrared Pulses

Two-dimensional organic-inorganic hybrid perovskites (2DHPs) are natural quantum-well-like materials, in which strong quantum and dielectric confinement effects due to the organic spacers give rise to tightly bound excitons with large binding energy. To examine the mutual interactions between the organic spacer cations and the inorganic charge-residing octahedral framework in 2DHPs, here we perform femtosecond pump-probe spectroscopy by direct vibrational pumping of the organic spacers, followed by a visible-to-ultraviolet probe covering their excitonic resonances. Measurements on prototypical lead-bromide based 2DHP compounds, (BA) 2 ⁢PbBr 4 and (BA) 2 ⁢(FA)⁢Pb 2 ⁢Br 7 (BA+ = butylammonium; FA + = formamidinium), reveal two distinct regimes of the temporal response. The first regime is dominated by a pump-induced transient expansion of the organic spacer layers that reduces the exciton oscillator strength, whereas the second regime arises from pump-induced lattice heating effects primarily associated with a spectral shift of the exciton energy. In addition, vibrational excitation enhances the biexciton emission, which we attribute to a stronger intralayer exciton confinement as well as vibrationally induced exciton detrapping from defect states. Finally, our study provides fundamental insights regarding the impact of organic spacers on excitons in 2DHPs, as well as the excited-state dynamics and vibrational energy dissipation in these structurally diverse materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Phonon Screening of Excitons in Atomically Thin Semiconductors

Atomically thin semiconductors, encompassing both 2D materials and quantum wells, exhibit a pronounced enhancement of excitonic effects due to geometric confinement. Consequently, these materials have become foundational platforms for the exploration and utilization of excitons. Recent ab initio studies have demonstrated that phonons can substantially screen electron-hole interactions in bulk semiconductors and strongly modify the properties of excitons. While excitonic properties of atomically thin semiconductors have been the subject of extensive theoretical investigations, the role of phonon screening on excitons in atomically thin structures remains unexplored. In this Letter, we demonstrate via ab initio GW-Bethe-Salpeter equation calculations that phonon screening can have a significant impact on optical excitations in atomically thin semiconductors. We further show that the degree of phonon screening can be tuned by structural engineering. We focus on atomically thin GaN quantum wells embedded in AlN and identify specific phonons in the surrounding material, AlN, that dramatically alter the lowest-lying exciton in monolayer GaN via screening. Our studies provide new intuition beyond standard models into the interplay among structural properties, phonon characteristics, and exciton properties in atomically thin semiconductors, and have implications for future experiments.

2-dimensional systems↗
DOE OSTI2025

Quantum confining excitons with an electrostatic moiré superlattice

Quantum confining excitons has been a persistent challenge in the pursuit of strong exciton interactions and quantum light generation. Unlike electrons, which can be readily controlled via electric fields, imposing strong nanoscale potentials on excitons to enable quantum confinement has proven challenging. In this study, we utilize piezoelectric force microscopy to image the domain structures of twisted hexagonal boron nitride (h – BN), revealing evidence of strong in-plane electric fields at the domain boundaries. By placing a monolayer MoSe 2 only one to two nanometers away from the twisted h – BN interface, we observe energy splitting of neutral excitons and Fermi polarons by several millielectronvolts at the moiré domain boundaries. By directly correlating local structural and optical properties, we attribute such observations to excitons confined in a nanoscale one-dimensional electrostatic potential created by the strong in-plane electric fields at the moiré domain boundaries. Intriguingly, this 1D quantum confinement results in pronounced polarization anisotropy in the excitons’ reflection and emission, persistent to temperatures as high as ~80 Kelvins. Furthermore, these findings open new avenues for exploring and controlling strongly interacting excitons for classical and quantum optoelectronics.

2-dimensional systems↗
DOE OSTI2020

Ultrafast Exciton Transport with a Long Diffusion Length in Layered Perovskites with Organic Cation Functionalization

Abstract Layered perovskites have been employed for various optoelectronic devices including solar cells and light‐emitting diodes for improved stability, which need exciton transport along both the in‐plane and the out‐of‐plane directions. However, it is not clear yet what determines the exciton transport along the in‐plane direction, which is important to understand its impact toward electronic devices. Here, by employing both steady‐state and transient photoluminescence mapping, it is found that in‐plane exciton diffusivities in layered perovskites are sensitive to both the number of layers and organic cations. Apart from exciton–phonon coupling, the octahedral distortion is revealed to significantly affect the exciton diffusion process, determined by temperature‐dependent photoluminescence, light‐intensity‐dependent time‐resolved photoluminescence, and density function theory calculations. A simple fluorine substitution to phenethylammonium for the organic cations to tune the structural rigidity and octahedral distortion yields a record exciton diffusivity of 1.91 cm 2 s −1 and a diffusion length of 405 nm along the in‐plane direction. This study provides guidance to manipulate exciton diffusion by modifying organic cations in layered perovskites.

Xiao, Xun↗
DOE OSTI2021

How the Size and Density of Charge-Transfer Excitons Depend on Heterojunction’s Architecture

We have characterized the size, intensity, density, and distribution of charge-transfer (CT) excitons as a function of the acceptor–donor architecture of prototypical organic interfaces. This characterization was done by computational analysis of 17 models of varying numbers, positions, and orientations of the donor and acceptor molecules. The models’ building blocks were phenyl-C61-butyric acid methyl ester (PCBM) fullerene acceptors and dual-band donor polymers composed of thiophene, benzothiadiazole, and benzotriazole subunits. The electronic structure of the donor–acceptor complexes was computed with the time-dependent long-range-corrected density-functional tight-binding method and analyzed with the fragment-based one-electron transition density matrix. In all models, the complexes with edge-on orientation have denser spectra of low-energy CT states lying below the absorption bands compared to the complexes with face-on orientation. This CT-state distribution in edge-on complexes provides a gate to efficiently populate cold CT excitons. Moreover, the cold CT excitons have a higher degree of charge separation in the edge-on than in the face-on complexes. The CT amount and the CT exciton size generally increase with the energy of the CT states, although the electron remains localized on a single molecule in cold CT states. Delocalization over two PCBM molecules was observed for high-energy CT states. The exciton size also depends on the orientation. Larger excitons are produced by the delocalization of the electrons perpendicularly to the interface. When the delocalization is parallel, the smaller electron–hole distances yield moderately sized CT excitons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exciton-Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands

Some ligand-nanocrystal combinations exhibit rapid cooling of highly excited electronic states while other nanocrystal/shell combinations do not appear to have this effect. There remains a need to identify the distinguishing properties of ligand-nanocrystal interactions that avoid such rapid relaxation processes to guide the design of colloidal quantum dots (QDs) that take advantage of multiple exciton generation or hot-carrier extraction processes. Here, we use mid-infrared transient absorption spectroscopy to investigate the influence that carboxylate ligands with distinct excited state surface chemistries has on exciton-phonon coupling and hot exciton relaxation in PbS quantum dot (QD) films. Our findings reveal that despite significant differences in the excited state surface chemistry of oleate (OA) and iodide/mercaptopropionic acid (I-/MPA) ligands, PbS QD films passivated with both ligand types exhibit identical electronic relaxation rates and exciton-phonon coupling strengths within experimental precision. The data suggest that the inorganic lattice is the principal source of exciton-phonon coupling that influences hot exciton relaxation, rather than the vibronic modes of carboxylate ligands. The size-dependent nature of the exciton-phonon coupling strength is consistent with the localization of charge on the QD surfaces, which enhances the mixing of electronic and nuclear coordinates particularly when the electronic states are more quantum confined in smaller nanocrystals.

14 SOLAR ENERGY↗
DOE OSTI2021

Imaging Charged Exciton Localization in van der Waals WSe 2 /MoSe 2 Heterobilayers

Exciton localization in transition-metal dichalcogenide monolayers is behind a variety of interesting phenomena and applications, including broad-spectrum solar cells and singlephoton emissions. Strain fields at the periphery of topographically distinct features such as nanoscopic bubbles were recently associated with localized charge-neutral excitons. Here, we use tip-enhanced photoluminescence (PL) to visualize excitons in WSe 2 /MoSe 2 heterobilayers (HBL). We find strong optical emission from charged excitons, particularly positively charged trions, in HBL supported by interlayer charge transfer. Our results reveal strong trion confinement, with a localization length scale comparable to the trion size, at the apex region inside individual nanoscopic bubbles. Nano-PL mapping also shows sub-10 nm spatial variations in the localized trion emission spectra, which stem from atomic-scale potential energy fluctuations. These findings demonstrate the possibility of confining charged exciton complexes that are electrically tunable, opening up further opportunities to probe many-body exciton physics, and to explore additional possible sites for strong exciton localization that can lead to quantum emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Phonon-exciton Interactions in WSe 2 under a quantizing magnetic field

Strong many-body interaction in two-dimensional transitional metal dichalcogenides provides a unique platform to study the interplay between different quasiparticles, such as prominent phonon replica emission and modified valley-selection rules. A large out-of-plane magnetic field is expected to modify the exciton-phonon interactions by quantizing excitons into discrete Landau levels, which is largely unexplored. Here, we observe the Landau levels originating from phonon-exciton complexes and directly probe exciton-phonon interaction under a quantizing magnetic field. Phonon-exciton interaction lifts the inter-Landau-level transition selection rules for dark trions, manifested by a distinctively different Landau fan pattern compared to bright trions. This allows us to experimentally extract the effective mass of both holes and electrons. The onset of Landau quantization coincides with a significant increase of the valley-Zeeman shift, suggesting strong many-body effects on the phonon-exciton interaction. Our work demonstrates monolayer WSe 2 as an intriguing playground to study phonon-exciton interactions and their interplay with charge, spin, and valley.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Enhanced nonlinear interaction of polaritons via excitonic Rydberg states in monolayer WSe 2 .

Strong optical nonlinearities play a central role in realizing quantum photonic technologies. Exciton-polaritons, which result from the hybridization of material excitations and cavity photons, are an attractive candidate to realize such nonlinearities. While the interaction between ground state excitons generates a notable optical nonlinearity, the strength of such interactions is generally not sufficient to reach the regime of quantum nonlinear optics. Excited states, however, feature enhanced interactions and therefore hold promise for accessing the quantum domain of single-photon nonlinearities. Here we demonstrate the formation of exciton-polaritons using excited excitonic states in monolayer tungsten diselenide (WSe 2 ) embedded in a microcavity. The realized excited-state polaritons exhibit an enhanced nonlinear response ~[Formula: see text] which is ~4.6 times that for the ground-state exciton. The demonstration of enhanced nonlinear response from excited exciton-polaritons presents the potential of generating strong exciton-polariton interactions, a necessary building block for solid-state quantum photonic technologies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗