Localized Excitons Research Articles

Polarization and Charge-Separation of Moiré Excitons in van der Waals Heterostructures.

Twisted transition metal dichalcogenide (TMD) bilayers exhibit periodic moiré potentials, which can trap excitons at certain high-symmetry sites. At small twist angles, TMD lattices undergo an atomic reconstruction, altering the moiré potential landscape via the formation of large domains, potentially separating the charges in-plane and leading to the formation of intralayer charge-transfer (CT) excitons. Here, we employ a microscopic, material-specific theory to investigate the intralayer charge-separation in atomically reconstructed MoSe2-WSe2 heterostructures. We identify three distinct and twist-angle-dependent exciton regimes including localized Wannier-like excitons, polarized excitons, and intralayer CT excitons. We calculate the moiré site hopping for these excitons and predict a fundamentally different twist-angle-dependence compared to regular Wannier excitons - presenting an experimentally accessible key signature for the emergence of intralayer CT excitons. Furthermore, we show that the charge separation and its impact on the hopping can be efficiently tuned via dielectric engineering.

The interplay of excitonic delocalization and vibrational localization in optical lineshapes: A variational polaron approach.

The dynamics of molecular excitonic systems are complicated by a competition between electronic coupling (which drives delocalization) and vibrational-electronic (vibronic) interactions (which tend to encourage electronic localization). A particular challenge of molecular systems is that they typically possess a large number of independent vibrations, with frequencies often spanning the entire spectrum of relevant electronic energy gaps. Recent spectroscopic observations and numerical simulations on a water-soluble chlorophyll-binding protein (WSCP) reveal a transition between two regimes of vibronic behavior, a Redfield-like regime in which low-frequency vibrations respond to a delocalized excitonic state, and a Förster-like regime where high-frequency vibrations act as incoherent excitations on individual pigments. Although numerical simulations can reproduce these effects, there is a need for a simple, systematic theory that accurately describes the smooth transition between these two regimes in experimental spectra. Here we address this challenge by generalizing the variational polaron transform approach of [Bloemsma et al., Chem. Phys. 481, 250 (2016)] to include arbitrary bath densities for systems with or without symmetry. We benchmark this theory against both numerical matrix-diagonalization methods and experimental 77K fluorescence spectra for two WSCP variants, obtaining quite satisfactory agreement in both cases. We apply this theory to offer an explanation for the large loss in apparent electronic coupling in the WSCP Q57K mutant and to examine the likely impact of the interplay between excitonic delocalization and vibrational localization on vibrational sideband shapes and apparent coupling strengths in high-resolution optical spectra for chlorophyll-protein complexes such as WSCP.

Interaction-Induced Crystalline Topology of Excitons.

We apply the topological theory of symmetry indicators to interaction-induced exciton band structures in centrosymmetric semiconductors. Crucially, we distinguish between the topological invariants inherited from the underlying electron and hole bands and those that are intrinsic to the exciton wave function itself. Focusing on the latter, we show that there exists a class of exciton bands for which the maximally localized exciton Wannier states are shifted with respect to the electronic Wannier states by a quantized amount; we call these excitons shift excitons. Our analysis explains how the exciton spectrum can be topologically nontrivial and sustain exciton edge states in open boundary conditions even when the underlying noninteracting bands have a trivial atomic limit. We demonstrate the presence of shift excitons as the lowest energy neutral excitations of the Su-Schrieffer-Heeger model in its trivial phase when supplemented by local two-body interactions.

Probing the Nature of Single-Photon Emitters in a WSe2 Monolayer by Magneto-Photoluminescence Spectroscopy.

Monolayer transition metal dichalcogenides (TMDs) have emerged as promising materials to generate single-photon emitters (SPEs). While there are several previous reports in the literature about TMD-based SPEs, the precise nature of the excitonic states involved in them is still under debate. Here, we use magneto-optical techniques under in-plane and out-of-plane magnetic fields to investigate the nature of SPEs in WSe2 monolayers on glass substrates under different strain profiles. Our results reveal important changes on the exciton localization and, consequently, on the optical properties of SPEs. Remarkably, we observe an anomalous PL energy redshift with no significant changes of photoluminescence (PL) intensity under an in-plane magnetic field. We present a model to explain this redshift based on intervalley defect excitons under a parallel magnetic field. Overall, our results offer important insights into the nature of SPEs in TMDs, which are valuable for future applications in quantum technologies.

Moiré-engineered light-matter interactions in MoS2/WSe2 heterobilayers at room temperature

Moiré superlattices in van der Waals heterostructures represent a highly tunable quantum system, attracting substantial interest in both many-body physics and device applications. However, the influence of the moiré potential on light-matter interactions at room temperature has remained largely unexplored. In our study, we demonstrate that the moiré potential in MoS2/WSe2 heterobilayers facilitates the localization of interlayer exciton (IX) at room temperature. By performing reflection contrast spectroscopy, we demonstrate the importance of atomic reconstruction in modifying intralayer excitons, supported by the atomic force microscopy experiment. When decreasing the twist angle, we observe that the IX lifetime becomes longer and light emission gets enhanced, indicating that non-radiative decay channels such as defects are suppressed by the moiré potential. Moreover, through the integration of moiré superlattices with silicon single-mode cavities, we find that the devices employing moiré-trapped IXs exhibit a significantly lower threshold, one order of magnitude smaller compared to the device utilizing delocalized IXs. These findings not only encourage the exploration of many-body physics in moiré superlattices at elevated temperatures but also pave the way for leveraging these artificial quantum materials in photonic and optoelectronic applications.

Investigating the exciton dynamics in InGaN/GaN core-shell nanorods using time-resolved cathodoluminescence.

This study examines the exciton dynamics in InGaN/GaN core-shell nanorods using time-resolved cathodoluminescence (TRCL), which provides nanometer-scale lateral spatial and tens of picoseconds temporal resolutions. The focus is on thick (>20 nm) InGaN layers on the non-polar, semi-polar and polar InGaN facets, which are accessible for study due to the unique nanorod geometry. Spectrally integrated TRCL decay transients reveal distinct recombination behaviours across these facets, indicating varied exciton lifetimes. By extracting fast and slow lifetime components and observing their temperature trends along with those of the integrated and peak intensity, the differences in behaviour were linked to variations in point defect density and the degree and density of localisation centres in the different regions. Further analysis shows that the non-polar and polar regions demonstrate increasing lifetimes with decreasing emission energy, attributed to an increase in the depth of localisation. The semi-polar facet instead showed a spectral independence of the lifetime which could not be rationalised by an absence of exciton localisation. This investigation provides insights into the intricate exciton dynamics in InGaN/GaN nanorods, offering valuable information for the design and development of optoelectronic devices.

Coexistence of the Band Filling Effect and Trap-State Filling in the Size-Dependent Photoluminescence Blue Shift of MAPbBr3 Nanoparticles.

The size-dependent photoluminescence (PL) blue shift in organometal halide perovskite nanoparticles has traditionally been attributed to quantum confinement effects (QCEs), irrespective of nanoparticle size. However, this interpretation lacks rigor for nanoparticles with diameters exceeding the exciton Bohr radius (rB). To address this, we investigated the PL of MAPbBr3 nanoparticles (MNPs) with diameters ranging from ~2 to 20 nm. By applying the Brus equation and Burstein-Moss theory to fit the PL and absorption blue shifts, we found that for MNPs larger than rB, the blue shift is not predominantly governed by QCEs but aligns closely with the band filling effect. This was further corroborated by a pronounced excitation-density-dependent PL blue shift (Burstein-Moss shift) at high photoexcitation densities. Additionally, trap-state filling was also found to be not a negligible origin of the PL blue shift, especially for the smaller MNPs. The time-resolved PL spectra (TRPL) and excitation-density-dependent TRPL are collected to support the coexistence of both filling effects by the high initial carrier density (~1017-1018 cm-3) and the recombination dynamics of localized excitons and free carriers in the excited state. These findings underscore the combined role of the band filling and trap-state filling effects in the size-dependent PL blue shift for solution-prepared MNPs with diameters larger than rB, offering new insights into the intrinsic PL blue shift in organometal halide perovskite nanoparticles.

Frenkel and Charge‐Transfer Excitonic Couplings Strengthened by Thiophene‐Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency

AbstractOvercoming the trade‐off between short‐circuited current (Jsc) and open‐circuited voltage (Voc) is important to achieving high‐efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge‐transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE‐CT excitonic coupling (tLE‐CT) via a simple but effective strategy that the 2‐chlorothiophene (2Cl−Th) solvent utilizes in the treatment of OSC active‐layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl−Th solvent initiates tighter intermolecular interactions with non‐fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over‐aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl−Th treated blend efficiently strengthen tLE‐CT, which not only promotes exciton splitting but also reduces non‐radiative recombination. The champion efficiencies of 19.8 % (small‐area) with superior operational reliability (T80: 586 hours) and 17.0 % (large‐area) were yielded in 2Cl−Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade‐off between Jsc and Voc, which can productively promote the development of the OSC field.

Frenkel and Charge-Transfer Excitonic Couplings Strengthened by Thiophene-Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency.

Overcoming the trade-off between short-circuited current (Jsc) and open-circuited voltage (Voc) is important to achieving high-efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge-transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE-CT excitonic coupling (tLE-CT) via a simple but effective strategy that the 2-chlorothiophene (2Cl-Th) solvent utilizes in the treatment of OSC active-layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl-Th solvent initiates tighter intermolecular interactions with non-fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over-aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl-Th treated blend efficiently strengthen tLE-CT, which not only promotes exciton splitting but also reduces non-radiative recombination. The champion efficiencies of 19.8 % (small-area) with superior operational reliability (T80: 586 hours) and 17.0 % (large-area) were yielded in 2Cl-Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade-off between Jsc and Voc, which can productively promote the development of the OSC field.

Moiré superlattices in twisted two-dimensional halide perovskites.

Moiré superlattices have emerged as a new platform for studying strongly correlated quantum phenomena, but these systems have been largely limited to van der Waals layer two-dimensional materials. Here we introduce moiré superlattices leveraging ultrathin, ligand-free halide perovskites, facilitated by ionic interactions. Square moiré superlattices with varying periodic lengths are clearly visualized through high-resolution transmission electron microscopy. Twist-angle-dependent transient photoluminescence microscopy and electrical characterizations indicate the emergence of localized bright excitons and trapped charge carriers near a twist angle of ~10°. The localized excitons are accompanied by enhanced exciton emission, attributed to an increased oscillator strength by a theoretically predicted flat band. This research showcases the promise of two-dimensional perovskites as unique room-temperature moiré materials.

Strain fingerprinting of exciton valley character in 2D semiconductors

Intervalley excitons with electron and hole wavefunctions residing in different valleys determine the long-range transport and dynamics observed in many semiconductors. However, these excitons with vanishing oscillator strength do not directly couple to light and, hence, remain largely unstudied. Here, we develop a simple nanomechanical technique to control the energy hierarchy of valleys via their contrasting response to mechanical strain. We use our technique to discover previously inaccessible intervalley excitons associated with K, Γ, or Q valleys in prototypical 2D semiconductors WSe2 and WS2. We also demonstrate a new brightening mechanism, rendering an otherwise “dark” intervalley exciton visible via strain-controlled hybridization with an intravalley exciton. Moreover, we classify various localized excitons from their distinct strain response and achieve large tuning of their energy. Overall, our valley engineering approach establishes a new way to identify intervalley excitons and control their interactions in a diverse class of 2D systems.

Pressure-controlled free exciton and self-trapped exciton emission in quasi-one-dimensional hybrid lead bromides

Hybrid metal halides represent a novel type of semiconductor light emitters with intriguing excitonic emission properties, including free exciton emission and self-trapped exciton emission. Achieving precise control over these two excitonic emissions in hybrid metal halides is highly desired yet remains challenging. Here, the complete transformation from intrinsically broadband self-trapped exciton emission to distinctively sharp free exciton emission in a quasi-one-dimensional hybrid metal halide (C2H10N2)8[Pb4Br18]·6Br with a ribbon width of n = 4, is successfully achieved based on high-pressure method. During compression, pressure-induced phonon hardening continuously reduces exciton–phonon coupling, therefore suppressing excitonic localization and quenching the original self-trapped exciton emission. Notably, further compression triggers excitonic delocalization to induce intense free exciton emission, accompanied with reduced carrier effective masses and improved charge distribution. Controlled high-pressure investigations indicate that the ribbon width of n > 2 is necessary to realize excitonic delocalization and generate free exciton emissions in similar quasi-one-dimensional hybrid metal halides. This work presents an important photophysical process of excitonic transitions from self-trapped exciton emission to free exciton emission in quasi-one-dimensional hybrid metal halides without chemical regulation, promoting the rational synthesis of hybrid metal halides with desired excitonic emissions.

Exciton-harvesting enabled efficient charged particle detection in zero-dimensional halides

Materials for radiation detection are critically important and urgently demanded in diverse fields, starting from fundamental scientific research to medical diagnostics, homeland security, and environmental monitoring. Low-dimensional halides (LDHs) exhibiting efficient self-trapped exciton (STE) emission with high photoluminescence quantum yield (PLQY) have recently shown a great potential as scintillators. However, an overlooked issue of exciton-exciton interaction in LDHs under ionizing radiation hinders the broadening of its radiation detection applications. Here, we demonstrate an exceptional enhancement of exciton-harvesting efficiency in zero-dimensional (0D) Cs3Cu2I5:Tl halide single crystals by forming strongly localized Tl-bound excitons. Because of the suppression of non-radiative exciton-exciton interaction, an excellent α/β pulse-shape-discrimination (PSD) figure-of-merit (FoM) factor of 2.64, a superior rejection ratio of 10−9, and a high scintillation yield of 26 000 photons MeV−1 under 5.49 MeV α-ray are achieved in Cs3Cu2I5:Tl single crystals, outperforming the commercial ZnS:Ag/PVT composites for charged particle detection applications. Furthermore, a radiation detector prototype based on Cs3Cu2I5:Tl single crystal demonstrates the capability of identifying radioactive 220Rn gas for environmental radiation monitoring applications. We believe that the exciton-harvesting strategy proposed here can greatly boost the applications of LDHs materials.

(Invited) Exciton Dissociation in Mixed-Dimensionality SWCNT-Based Heterojunctions

Quantum-confined semiconductors provide highly tunable optical and electrical properties for a wide variety of emerging applications. Semiconducting single-walled carbon nanotubes (s-SWCNTs) have shown tremendous potential in applications ranging from digital logic, biological imaging, quantum information processing, photovoltaics, and thermoelectric energy harvesting. Energy harvesting applications rely critically upon the creation of tailored interfaces that enable the movement of energetic species (excitons, electrons, holes) in specified directions. In this talk, I will discuss the use of a variety of rationally designed “mixed-dimensionality” heterojunctions between s-SWCNTs and transition metal dichalcogenide (TMDC) monolayers to harvest visible/near-infrared photons and convert these excitations into long-lived charge-separated states. Type-II heterojunctions between s-SWCNTs and TMDCs enable rapid exciton dissociation and microsecond charge-separated state lifetimes. We have developed new TMDC/SWCNT/TMDC trilayer architectures that enable charge transfer cascades for improving charge separation yield and lifetime. These trilayer architectures allow us to probe out-of-plane carrier diffusion in the nanotube layer and the degree to which bound interfacial excitons impact the photophysics in these mixed-dimensionality heterostructures. I will also discuss the methodology by which we attempt to quantify the photoinduced exciton dissociation quantum yields in these nanoscale heterostructures. Using several heterostructure results, we are attempting to narrow in on appropriate ways to quantify the local dielectric constant and exciton size in both the SWCNT and TMDC components, each of which impact the estimated charge carrier yields. Taken together, these studies provide fundamental insights into the links between ground-state thermodynamics and excited-state dynamics for model nanoscale heterojunctions used to harvest solar energy and produce long-lived charge-separated states.

Pressure‐Tuning Localized Excitons Toward Enhanced Emission, Photocurrent Enhancement and Piezochromism in Unconventional ACI‐Type 2D Hybrid Perovskites

Simultaneous enhancement of free excitons (FEs) emission and self‐trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI‐type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5‐fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb‐I‐Pb angles between two halide octahedra under high pressure indeed determines the pressure‐tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure‐optical relationships of ACI‐type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure‐suppressed nonradiative recombination.

Pressure-Tuning Localized Excitons Toward Enhanced Emission, Photocurrent Enhancement and Piezochromism in Unconventional ACI-Type 2D Hybrid Perovskites.

Simultaneous enhancement of free excitons (FEs) emission and self-trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI-type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5-fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb-I-Pb angles between two halide octahedra under high pressure indeed determines the pressure-tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure-optical relationships of ACI-type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure-suppressed nonradiative recombination.

All-optical temporal logic gates in localized exciton polaritons

Exciton polaritons—quasi-particle excitations consisting of strongly coupled photons and excitons—present fascinating possibilities for photonic circuits, owing to their strong nonlinearity, ultrafast reaction times and their ability to form macroscopic quantum states at room temperature via non-equilibrium condensation. Past implementations of transistors and logic gates with exciton polaritons have been mostly realized using the spatial propagation of polariton fluids, which place high demands on the fabrication of the microcavities and typically require complex manipulations. In this work we have implemented the full set of logical gate functionalities (that is, temporal AND, OR and NOT gates) in localized exciton polaritons at room temperature, on the basis of precisely controlling the interplay between polariton condensate and exciton reservoir dynamics, using a two-pulse excitation scheme. The dynamics intrinsically covers the cascadability required by the logical operations, enabling efficient information processing without the need for spatial flow. The temporal polariton logic gates demonstrate advantages in ultrafast switching, universality and simplified compatibility with other dimensional controls, showing great potential for building polariton logic networks in strongly coupled light–matter systems.

Strain-induced modulation of the band structure of GaAs/GaSb/GaAs core-dual-shell nanowires

The amalgamation of high-strained core/shell geometries in nanowire (NW) heterostructures with bandgap engineering enables the systems with novel transport and optical properties. Herein, the lattice-mismatch-high construction GaAs/GaSb/GaAs core-dual-shell (CDS) NWs were grown by molecular beam epitaxy (MBE), with a focus on exploring the impact of strain on their bandgap characteristics. Interestingly, the high stain between GaSb and GaAs leads to the surface roughening that favors Stranski-Krastanov (SK) mode growth, and coherent GaSb islands on GaAs NWs form plastically relaxed mounds at the edges of the NW sidewall facets. Strain properties of GaAs/GaSb/GaAs CDS NWs have been investigated systematically by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman spectra. It is clearly revealed that the presence of different strains, with the strain diminished of GaSb shell layer in the large-scale NWs and amplified in the small-scale NWs. The optical properties of the GaAs/GaSb/GaAs CDS NWs were investigated by power- and temperature-dependent photoluminescence (PL) measurements, which reveal the emission properties with the exciton localization phenomenon. Our results on the unique optical properties of localized excitons in GaAs/GaSb/GaAs core-shell nanostructures open the way to the design of stable optoelectronic devices.

Characterization of quantum dot-like emitters in programmable arrays of nanowrinkles of 1L-WSe2

When combined with nanostructured substrates, two-dimensional semiconductors can be engineered with strain to tailor light–matter interactions on the nanoscale. Recently, room-temperature nanoscale exciton localization with controllable wrinkling in 1L-WSe2 was achieved using arrays of gold nanocones. Here, the characterization of quantum dot-like states and single-photon emitters in the 1L-WSe2/nanocone system is reported. The nanocones induce a wide range of strains, and as a result, a diverse ensemble of narrowband, potential single-photon emitters is observed. The distribution of emitter energies reveals that most reside in two spectrally isolated bands, leaving a less populated intermediate band that is spectrally isolated from the ensembles. The spectral isolation is advantageous for high-purity quantum light emitters, and anti-bunched emission from one of these states is confirmed up to 25 K. Although the spatial distribution of strain is expected to influence the orientation of the transition dipoles of the emitters, multimodal emission polarization anisotropy and atomic force microscopy reveal that the macroscopic orientation of the wrinkles is not a good predictor of dipole orientation. Finally, the emission is found to change with thermal cycling from 4 to 290 K and back to 4 K, highlighting the need to control factors such as temperature-induced strain to enhance the robustness of this quantum emitter platform. The initial characterization here shows that controlled nanowrinkles of 1L-WSe2 generate quantum light in addition to uncovering potential challenges that need to be addressed for their adoption into quantum photonic technologies.

The Role of Double Excitations in Exciton Dynamics of Multiazobenzenes: Trisazobenzenophane as a Test Case.

Molecular exciton dynamics underlie energy and charge transfer processes in organic multichromophoric systems. A particularly interesting class of the latter is multiphotochromic systems made of molecules capable of photochemical transformations. Exciton dynamics in assemblies of photoswitches have been recently investigated using either the molecular exciton model or supermolecular configuration interaction (CI) singles, both approaches being based on a semiempirical Hamiltonian and combined with surface hopping molecular dynamics. Here, we study how inclusion of double excitations in nonadiabatic dynamics simulations affects exciton dynamics of multiazobenzenes, using trisazobenzenophane as an example. We find that both CI singles and CI singles and doubles yield virtually the same time scale of dynamical exciton localization, ∼50 fs for the studied multiazobenzene. However, inclusion of double excitations considerably affects the excited state lifetimes and isomerization quantum yields.