Dark-bright Exciton Research Articles

Impact of Bright-Dark Exciton Thermal Population Mixing on the Brightness of CsPbBr3 Nanocrystals.

Understanding the interplay between bright and dark exciton states is crucial for deciphering the luminescence properties of low-dimensional materials. The origin of the outstanding brightness of lead halide perovskites remains elusive. Here, we analyze temperature-dependent time-resolved photoluminescence to investigate the population mixing between bright and dark exciton sublevels in individual CsPbBr3 nanocrystals in the intermediate confinement regime. We extract bright and dark exciton decay rates and show quantitatively that the decay dynamics can only be reproduced with second-order phonon transitions. Furthermore, we find that any exciton sublevel ordering is compatible with the most likely population transfer mechanism. The remarkable brightness of lead halide perovskite nanocrystals rather stems from a reduced asymmetry between bright-to-dark and dark-to-bright conversion originating from the peculiar second-order phonon-assisted transitions that freeze bright-dark conversion at low temperatures together with the very fast radiative recombination and favorable degeneracy of the bright exciton state.

Ultrafast many-body bright-dark exciton transition in anatase TiO2.

The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose-Einstein condensation, and light-energy harvesting. Anatase TiO2 with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe-Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO2. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron-phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron-hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright-dark exciton transitions sheds insights into applications of anatase TiO2 in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors.

Influence of Organic Spacer Cation on Dark Excitons in 2D Perovskites

AbstractThe organic spacer cation plays a crucial role in determining the exciton fine structure in 2D perovskites. Here, magneto‐optical spectroscopy is used to gain insight into the influence of the organic spacer on dark excitons in Ruddlesden–Popper (RP) perovskites. Using modest magnetic field strengths (<1.5 T), the optically forbidden dark exciton state can be identified and its emission properties significantly modulated via application of in‐plane magnetic fields, up to temperatures of 15 K. At low temperatures, an increase in collected photoluminescence efficiency of >30% is demonstrated, signifying the critical role of the dark exciton state for light‐emitting applications of 2D perovskites. The exciton fine structure and the degree of magnetic‐field‐induced mixing are significantly impacted by the choice of organic spacer cation, with 4–methoxyphenylethylammonium (MeO‐PEA) showing the largest effect due to larger bright–dark exciton splitting. This study distinguishes between interior (bulk) and surface dark‐exciton emission, showing that bright–dark exciton splitting differs between the interior and surface. The results emphasize the significance of the organic spacer cation in controlling the exciton fine structure in 2D perovskites and have important implications for the development of optoelectronic technology based on 2D perovskites.

Control of the Bright-Dark Exciton Splitting Using the Lamb Shift in a Two-Dimensional Semiconductor.

We investigate the exciton fine structure in atomically thin WSe_{2}-based van der Waals heterostructures where the density of optical modes at the location of the semiconductor monolayer can be tuned. The energy splitting Δ between the bright and dark exciton is measured by photoluminescence spectroscopy. We demonstrate that Δ can be tuned by a few meV as a result of a significant Lamb shift of the optically active exciton that arises from emission and absorption of virtual photons triggered by the vacuum fluctuations of the electromagnetic field. We also measure strong variations of the bright exciton radiative linewidth as a result of the Purcell effect. All these experimental results illustrate the strong sensitivity of the excitons to local vacuum field fluctuations. We find a very good agreement with a model that demonstrates the equivalence, for our system, of a classical electrodynamical transfer matrix formalism and quantum-electrodynamical approach. The bright-dark splitting control we demonstrate here in the weak light-matter coupling regime should apply to any semiconductor structures.

Layer-dependent exciton polarizability and the brightening of dark excitons in few-layer black phosphorus

The evolution of excitons from 2D to 3D is of great importance in photo-physics, yet the layer-dependent exciton polarizability hasn’t been investigated in 2D semiconductors. Here, we determine the exciton polarizabilities for 3- to 11-layer black phosphorus—a direct bandgap semiconductor regardless of the thickness—through frequency-resolved photocurrent measurements on dual-gate devices and unveil the carrier screening effect in relatively thicker samples. By taking advantage of the broadband photocurrent spectra, we are also able to reveal the exciton response for higher-index subbands under the gate electrical field. Surprisingly, dark excitons are brightened with intensity even stronger than the allowed transitions above certain electrical field. Our study not only sheds light on the exciton evolution with sample thickness, but also paves a way for optoelectronic applications of few-layer BP in modulators, tunable photodetectors, emitters and lasers.

Gradient Type‐II CdSe/CdSeTe/CdTe Core/Crown/Crown Heteronanoplatelets with Asymmetric Shape and Disproportional Excitonic Properties (Small 11/2023)

Multi-Crown Type-II Nanoplatelets In article number 2205729, Hilmi Volkan Demir and co-workers discuss the recombination dynamics of CdSe/CdSeTe/CdTe core/crown/crown nanoplatelets (NPLs) with a step-wise gradient electronic structure. The NPLs possess disproportional electron and hole wavefunction distributions, in which the activation/deactivation of direct and indirect channels is possible by adjusting the domains' geometry. These NPLs demonstrate exceptionally high two-photon absorption cross-section and low dark-bright exciton splitting energy.

Gradient Type-II CdSe/CdSeTe/CdTe Core/Crown/Crown Heteronanoplatelets with Asymmetric Shape and Disproportional Excitonic Properties.

Characterized by their strong 1D confinement and long-lifetime red-shifted emission spectra, colloidal nanoplatelets (NPLs) with type-II electronic structure provide an exciting ground to design complex heterostructures with remarkable properties. This work demonstrates the synthesis and optical characterization of CdSe/CdSeTe/CdTe core/crown/crown NPLs having a step-wise gradient electronic structure and disproportional wavefunction distribution, in which the excitonic properties of the electron and hole can be finely tuned through adjusting the geometry of the intermediate crown. The first crown with staggered configuration gives rise to a series of direct and indirect transition channels that activation/deactivation of each channel is possible through wavefunction engineering. Moreover, these NPLs allow for switching between active channels with temperature, where lattice contraction directly affects the electron-hole (e-h) overlap. Dominated by the indirect transition channels over direct transitions, the lifetime of the NPLs starts to increase at 9 K, indicative of low dark-bright exciton splitting energy. The charge transfer states from the two type-II interfaces promote a large number of indirect transitions, which effectively increase the absorption of low-energy photons critical for nonlinear properties. As a result, these NPLs demonstrate exceptionally high two-photon absorption cross-sections with the highest value of 12.9 × 106 GM and superlinear behavior.

Universal scaling laws for charge-carrier interactions with quantum confinement in lead-halide perovskites

Lead halide perovskites open great prospects for optoelectronics and a wealth of potential applications in quantum optical and spin-based technologies. Precise knowledge of the fundamental optical and spin properties of charge-carrier complexes at the origin of their luminescence is crucial in view of the development of these applications. On nearly bulk Cesium-Lead-Bromide single perovskite nanocrystals, which are the test bench materials for next-generation devices as well as theoretical modeling, we perform low temperature magneto-optical spectroscopy to reveal their entire band-edge exciton fine structure and charge-complex binding energies. We demonstrate that the ground exciton state is dark and lays several millielectronvolts below the lowest bright exciton sublevels, which settles the debate on the bright-dark exciton level ordering in these materials. More importantly, combining these results with spectroscopic measurements on various perovskite nanocrystal compounds, we show evidence for universal scaling laws relating the exciton fine structure splitting, the trion and biexciton binding energies to the band-edge exciton energy in lead-halide perovskite nanostructures, regardless of their chemical composition. These scaling laws solely based on quantum confinement effects and dimensionless energies offer a general predictive picture for the interaction energies within charge-carrier complexes photo-generated in these emerging semiconductor nanostructures.

Exciton fine structure of a single highly anisotropic CsPbBr3 nanocrystal

We measured the photoluminescence (PL) of single CsPbBr3 nanocrystals (NCs) that have a highly anisotropic shape and orthorhombic crystal phase. As the thickness of these NCs is much more smaller than the other two dimensions, they are also called nanoplatelets (NPLs). We obtain PL spectra characterized by doublets separated in energy by about 2 meV in average and showing orthogonal and linearly polarized polar lines. We identified these doublets as the two bright-exciton states of the exciton fine structure contained in the plane of the NPLs. By a comparison between theory and experiments, we were able to obtain fundamental parameters as tetragonal and orthorhombic crystal field. We measured and analysed the time-resolved PL evolution as a function of temperature of small ensemble of NPLs. We thus succeed at framing the experimental value of the bright-dark exciton splitting (5-7meV) that is slightly smaller than the theoretical value.

A Comparative Study of the Band-Edge Exciton Fine Structure in Zinc Blende and Wurtzite CdSe Nanocrystals

In this paper, we studied the role of the crystal structure in spheroidal CdSe nanocrystals on the band-edge exciton fine structure. Ensembles of zinc blende and wurtzite CdSe nanocrystals are investigated experimentally by two optical techniques: fluorescence line narrowing (FLN) and time-resolved photoluminescence. We argue that the zero-phonon line evaluated by the FLN technique gives the ensemble-averaged energy splitting between the lowest bright and dark exciton states, while the activation energy from the temperature-dependent photoluminescence decay is smaller and corresponds to the energy of an acoustic phonon. The energy splittings between the bright and dark exciton states determined using the FLN technique are found to be the same for zinc blende and wurtzite CdSe nanocrystals. Within the effective mass approximation, we develop a theoretical model considering the following factors: (i) influence of the nanocrystal shape on the bright-dark exciton splitting and the oscillator strength of the bright exciton, and (ii) shape dispersion in the ensemble of the nanocrystals. We show that these two factors result in similar calculated zero-phonon lines in zinc blende and wurtzite CdSe nanocrystals. The account of the nanocrystals shape dispersion allows us to evaluate the linewidth of the zero-phonon line.

2D Metal Halide Perovskites: A New Fascinating Playground for Exciton Fine Structure Investigations

Two-dimensional (2D) metal halide perovskites are natural quantum wells which consist of low bandgap metal-halide slabs, surrounded by organic spacers barriers. The quantum and dielectric confinements provided by the organic part lead to the extreme exciton binding energy which results in a huge enhancement of exciton fine structure in this material system. This makes 2D perovskites a fascinating playground for fundamental excitonic physics studies. In this review, we summarize the current understanding and quantification of the exciton fine structure in 2D perovskites. We discuss what is the role of exciton fine structure in the optical response of 2D perovskites and how it challenges our understanding of this fundamental excitation. Finally, we highlight some controversy related to particularly large bright-dark exciton states splitting and high efficiency of light emission from these materials. This can result from the unique synergy of excitonic and mechanical properties of 2D perovskites crystals.

Dark and Bright Excitons in Halide Perovskite Nanoplatelets.

Semiconductor nanoplatelets (NPLs), with their large exciton binding energy, narrow photoluminescence (PL), and absence of dielectric screening for photons emitted normal to the NPL surface, could be expected to become the fastest luminophores amongst all colloidal nanostructures. However, super‐fast emission is suppressed by a dark (optically passive) exciton ground state, substantially split from a higher‐lying bright (optically active) state. Here, the exciton fine structure in 2–8 monolayer (ML) thick Cs n − 1Pb n Br3n + 1 NPLs is revealed by merging temperature‐resolved PL spectra and time‐resolved PL decay with an effective mass model taking quantum confinement and dielectric confinement anisotropy into account. This approach exposes a thickness‐dependent bright–dark exciton splitting reaching 32.3 meV for the 2 ML NPLs. The model also reveals a 5–16 meV splitting of the bright exciton states with transition dipoles polarized parallel and perpendicular to the NPL surfaces, the order of which is reversed for the thinnest NPLs, as confirmed by TR‐PL measurements. Accordingly, the individual bright states must be taken into account, while the dark exciton state strongly affects the optical properties of the thinnest NPLs even at room temperature. Significantly, the derived model can be generalized for any isotropically or anisotropically confined nanostructure.

Brightening of dark excitons in single-walled carbon nanotubes: Investigation by many-body Green’s function theory

Optical excitations of the hybrids, which are assembled by coupling single-walled carbon nanotubes (SWCNTs) with organic molecules through van der Waals interactions, are studied using ab initio manybody Green’s function theory. We take the semiconducting (7,0) SWCNT, the squarylium and oligothiophene molecules as the example. The E11 and E22 absorption peaks of the (7,0) tube can be redshifted by tens of meV. Most importantly, the lowest dark exciton of the (7,0) tube at the lower-energy side of E11 can be brightened by the interaction between the nanotube and molecules. Position of this new satellite absorption peak is influenced by the type of adsorbed molecule. These findings may be useful for tuning the emission energy and emission efficiency of CNTs.

Brightening of dark excitons in 2D perovskites.

Optically inactive dark exciton states play an important role in light emission processes in semiconductors because they provide an efficient nonradiative recombination channel. Understanding the exciton fine structure in materials with potential applications in light-emitting devices is therefore critical. Here, we investigate the exciton fine structure in the family of two-dimensional (2D) perovskites (PEA)2SnI4, (PEA)2PbI4, and (PEA)2PbBr4. In-plane magnetic field mixes the bright and dark exciton states, brightening the otherwise optically inactive dark exciton. The bright-dark splitting increases with increasing exciton binding energy. Hot photoluminescence is observed, indicative of a non-Boltzmann distribution of the bright-dark exciton populations. We attribute this to the phonon bottleneck, which results from the weak exciton–acoustic phonon coupling in soft 2D perovskites. Hot photoluminescence is responsible for the strong emission observed in these materials, despite the substantial bright-dark exciton splitting.

Optically Driven Giant Superbunching from a Single Perovskite Quantum Dot

AbstractPhoton superbunching is a signature of a strong correlation between photons, which is a crucial resource needed in quantum communication and computation. As such, a superbunched photon source based on a material with high quantum efficiency, like cesium lead halide perovskite, is highly desirable. Utilizing the large dark–bright exciton splitting in CsPbBr3quantum dot (QD), the authors achieve a superbunching with a large g(2)(0) ≈ 30 from an optically driven single CsPbBr3QD emission at cryogenic temperature. The cascaded emission is identified as the cause of this superbunching by utilizing second‐order cross‐correlation measurement and exploring the excitation power and temperature dependence of the bunching level. The findings have immediate implications on the basic understanding of a single perovskite QD emission and its application as a quantum light source.

Spinorial formulation of the GW -BSE equations and spin properties of excitons in two-dimensional transition metal dichalcogenides

In many paradigmatic materials, like Transition Metal Dichalcogenides, the role played by the spin degrees of freedom is as important as the one played by the electron-electron interaction. Thus an accurate treatment of the two effects and of their interaction is necessary for an accurate and predictive study of the optical and electronic properties of these materials. Despite the GW-BSE approach correctly accounts for electronic correlations the spin-orbit coupling effect is often neglected or treated perturbatively. Recently spinorial formulations of GW-BSE have become available in different flavours in material-science codes. Still an accurate validation and comparison of different approaches is missing. In this work we go through the derivation of non collinear GW-BSE approach. The scheme is applied to transition metal dichalcogenides comparing perturbative and full spinorial approach. Our calculations reveal that dark-bright exciton splittings are generally improved when the spin orbit coupling is included non perturbatively. The exchange-driven intravalley mixing between the A and B exciton is found to be extremely important in the case of MoSe$_2$. We finally define the excitonic spin and use it to sharply analyze the spinorial properties of Transition Metal Dichalcogenides excitonic states.

Interplay of Bright Triplet and Dark Excitons Revealed by Magneto-Photoluminescence of Individual PbS/CdS Quantum Dots.

A low-temperature polarization-resolved magneto-photoluminescence experiment is performed on individual PbS/CdS core/shell quantum dots (QDs). The experiment enables a direct measurement of the exciton Landé g factor and the anisotropic zero-field splitting of the lowest emissive bright exciton triplet in PbS/CdS QDs. While anisotropic splittings of individual QDs distribute randomly in 104-325 μeV range, the exciton Landé g factors increase from 0.95 to 2.70 as the emission energy of the QD increases from 1.0 to 1.2eV. The tight-binding calculations allow to rationalize these trends as a direct consequence of reducing a cubic symmetry of QD via addition/removal of a few (<70) atoms from the surfaces of the PbS core. Furthermore, it is observed that while right (σ + ) and left (σ - ) circularly polarized photoluminescence (PL) peaks split linearly with magnetic field as expected for Zeeman effect, the energy splitting between X and Y linearly polarized PL peaks remains nearly unchanged. The theoretical study reveals rich and complex magnetic field-induced interplay of bright triplet and dark exciton states explaining this puzzling behavior. These findings fill the missing gaps in the understanding of lead salt QDs and provide foundation for development of classical and quantum light sources operating at telecommunication wavelengths.

Size-dependent dark exciton properties in cesium lead halide perovskite quantum dots.

The fine structure of the band edge exciton and the dark exciton photoluminescence (PL) are topics of significant interest in the research of semiconducting metal halide perovskite nanocrystals, with several conflicting reports on the level ordering of the bright and dark states and the accessibility of the emitting dark states. Recently, we observed the intense dark exciton PL in strongly confined CsPbBr3 nanocrystals at cryogenic temperatures, in contrast to weakly confined nanocrystals lacking dark exciton PL, which was explained by the confinement enhanced bright-dark exciton splitting. In this work, we investigated the size-dependence of the dark exciton photoluminescence properties in CsPbBr3 and CsPbI3 quantum dots in the strongly confined regime, showing the clear role of confinement in determining the bright-dark energy splitting (ΔEBD) and the dark exciton lifetime (τD). We observe the increase in both ΔEBD and τD with increasing quantum confinement in CsPbBr3 and CsPbI3 QDs, consistent with the earlier predictions on the size-dependence of ΔEBD and τD. Our results show that quantum confinement plays a crucial role in determining the accessibility to the dark exciton PL and its characteristics in metal halide perovskite nanocrystals.

First-principles many-body theory for charged and neutral excitations: Trion fine structure splitting in transition metal dichalcogenides

A hybrid theory which combines configuration interaction and Green's function approaches is proposed here to treat charged and neutral excitations. The theory is parameter free and reduces to the well-known Bethe-Salpeter equation (BSE) in the case of excitons. However, unlike the BSE, the theory can be applied to calculate any excitation beyond the exciton. As this type of computation is generally time consuming, we show that in the case of Wannier-type excitations, the localization in reciprocal space can be used to reduce the required computation load. We apply our approach to excitons and trions in ${\mathrm{WS}}_{2}$ and ${\mathrm{MoS}}_{2}$ transition metal dichalcogenides monolayers and obtain optical spectra, binding energies, and dark-bright exciton splitting in good agreement with experimental measurements. Moreover, in the case of ${\mathrm{WS}}_{2}$, we have found that the negative trion peak shows a fine structure splitting (FSS) of 15 meV which corresponds to the FSS for an isolated monolayer.

Lattice Disorder-Engineered Energy Splitting between Bright and Dark Excitons in CsPbBr3 Quantum Wires.

Excitons in nanostructured semiconductors often undergo strong electron-hole exchange interaction, resulting in bright-dark exciton splitting with the dark exciton usually being the lower energy state. This unfavorable state arrangement has become the major bottleneck for achieving high photoluminescence quantum yield (PLQY). However, the arrangement of dark and bright exciton states in lead halide perovskites is under intense debate due to the involvement of many complicated factors. We present here the first experimental evidence to demonstrate that the strain is a crucial factor in tuning the energy splitting of the bright and dark excitons, resulting in different PL properties.