Exciton States Research Articles

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.

Observation of Room-Temperature Exciton-Polariton Emission from Wide-Ranging 2D Semiconductors Coupled with a Broadband Mie Resonator.

Two-dimensional exciton-polaritons in monolayer transition metal dichalcogenides (TMDs) exhibit practical advantages in valley coherence, optical nonlinearities, and even bosonic condensation owing to their light-emission capability. To achieve robust exciton-polariton emission, strong photon-exciton couplings are required at the TMD monolayer, which is challenging due to its atomic thickness. High-quality (Q) factor optical cavities with narrowband resonances are an effective approach but typically limited to a specific excitonic state of a certain TMD material. Herein, we achieve on-demand exciton-polariton emission from a wide range of TMDs at room temperature by hybridizing excitons with broadband Mie resonances spanning the whole visible spectrum. By confining broadband light at the TMD monolayer, our one type of Mie resonator on different TMDs enables enhanced light-matter interactions with multiple excitonic states simultaneously. We demonstrate multi-Rabi splittings and robust polaritonic photoluminescence in monolayer WSe2, WS2, and MoS2. The hybrid system also shows the potential to approach the ultrastrong coupling regime.

Many-Exciton Quantum Dynamics in a Ruddlesden-Popper Tin Iodide.

We present a study on the many-body exciton interactions in a Ruddlesden-Popper tin halide, namely, (PEA)2SnI4 (PEA = phenylethylammonium), using coherent two-dimensional electronic spectroscopy. The optical dephasing times of the third-order polarization observed in these systems are determined by exciton many-body interactions and lattice fluctuations. We investigate the excitation-induced dephasing (EID) and observe a significant reduction of the dephasing time with increasing excitation density as compared to its lead counterpart (PEA)2PbI4, which we have previously reported in a separate publication [J. Chem. Phys.2020, 153, 164706]. Surprisingly, we find that the EID interaction parameter is four orders of magnitude higher in (PEA)2SnI4 than that in (PEA)2PbI4. This increase in the EID rate may be due to exciton localization arising from a more statically disordered lattice in the tin derivative. This is supported by the observation of multiple closely spaced exciton states and the broadening of the linewidth with increasing population time (spectral diffusion), which suggests a static disordered structure relative to the highly dynamic lead-halide. Additionally, we find that the exciton nonlinear coherent lineshape shows evidence of a biexcitonic state with low binding energy (<10 meV) not observed in the lead system. We model the lineshapes based on a stochastic scattering theory that accounts for the interaction with a nonstationary population of dark background excitations. Our study provides evidence of differences in the exciton quantum dynamics between tin- and lead-based Ruddlesden-Popper metal halides (RPMHs) and links them to the exciton-exciton interaction strength and the static disorder aspect of the crystalline structure.

Determining Band Splitting and Spin-Flip Dynamics in Monolayer MoS2.

Femtosecond helicity-resolved pump-probe spectroscopy is performed to study the spin and valley dynamics in monolayer (ML) MoS2. Both the bright to dark intravalley exciton transition (∼50 fs) and the reverse transition process (<50 fs) are directly monitored. It suggests that the bright exciton state of ML MoS2 is lower in energy than the dark one, which is also confirmed by observing the temperature-dependent co-polarized photobleaching dynamics of A and B excitons. Furthermore, the band splitting in the conduction band of ML MoS2 with a value of 15 ± 0.3 meV is determined by fitting the temperature-dependent ratios of the population in bright and dark states using the Boltzmann distribution law. Such minor band splitting allows the phonon-mediated intravalley spin-flip to even occur from the lower to the upper conduction band within tens of femtoseconds, which will have non-negligible effects on the performance of these ML MoS2-based optoelectronic and photonic devices.

Quantum Phase Transitions of Interlayer Excitons in van der Waals Heterostructures

Quantum phases of interlayer excitons (IXs) in van der Waals heterostructures (vdWHs) play a critical role in determining the fundamental properties of these structures. However, quantum phase transitions between free state and self‐trapped state of IXs remain poorly understood. Herein, the physical pictures for quantum transitions of IXs stemming from the IX–interface optical phonon coupling are explored. The critical boundaries of the phase transitions among free, light, and heavy self‐trapped states are given and the dependence of boundaries on the structural parameters of vdWHs is discussed, implying the controllability of these IXs states in vdWHs. In order to distinguish different quantum phases further, a strategy that multiphonon Raman scattering mediated by these exciton states is proposed. It is found find that multiphonon overtones appear in Raman spectra for the self‐trapped states and not for free states, which clarifies the long‐standing puzzle that free exciton can induce multiphonon Raman processes. The results lay the significant theoretical foundation for understanding the quantum phases of IX and their modulation in vdWHs.

Exciton fine structure in twisted transition metal dichalcogenide heterostructures

Moiré superlattices of transition metal dichalcogenide (TMD) heterostructures give rise to rich excitonic phenomena associated with the interlayer twist angle. Theoretical calculations of excitons in such systems are typically based on model moiré potentials that mitigate the computational cost. However, predictive understanding of the electron-hole coupling dominating the excitations is crucial to realize the twist-induced modifications of the optical selection rules. In this work, we use many-body perturbation theory to evaluate the relation between twist angle and exciton properties in TMD heterostructures. We present an approach for unfolding excitonic states from the moiré Brillouin zone onto the separate-layer ones. Applying this method to a large-angle twisted MoS2/MoSe2 bilayer, we find that the optical spectrum is dominated by mixed electron–hole transitions with different momenta in the separate monolayers, leading to unexpected hybridization between interlayer and intralayer excitons. Our findings offer a design pathway for exciton layer-localization in TMD heterostructures.

Excitonic Effect Drives Ultrafast Transition in Two-Dimensional Transition Metal Dichalcogenides.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) are ideal platforms for exploring excitonic physics because of the tightly bound excitons. In this work, we observed the onset of band-edge exciton formation in monolayer MoS2 (WS2) and bilayer MoS2-WS2 by measuring the transient optical response upon excitation with ultrashort laser pulses. In addition to wavelength dependence on excitation under nonresonant excitation, we found that the onset of band-edge exciton formation in monolayer MoS2 (WS2) pumped in the exciton state is significantly faster than that with pumping in the nonexciton state, which could be attributed to the effective transition between exciton states induced by the excitonic effect. Besides, the onset of band-edge exciton formation in van der Waals heterostructures is similar to that for monolayer TMDCs regardless of charge transfer at the interface. Our work contributes to a better understanding of exciton dynamics in 2D TMDCs, providing a solid basis of the rational design of the 2D optoelectronic applications based on TMDCs.

Efficient two-dimensional Fraunhofer diffraction pattern via electron spin coherence

In this letter, we have discussed the two-dimensional diffraction pattern via electron spin coherence in a GaAs quantum dot. Impulsive stimulated Raman excitation utilizing coherent optical fields is employed for the purpose of regulating the electron spin coherence within a charged ensemble of GaAs quantum dots, by means of an intermediate charged exciton (trion) state. We show that for the coupling two-dimensional standing wave (SW) field in the x and y directions, the two-dimensional Fraunhofer pattern can be formed for a weak probe light. By using the experimental parameters and controlling the Rabi frequency of the SW field and relative phase between applied lights, the symmetry and asymmetry diffraction pattern are obtained for the weak probe light due to the four-wave mixing mechanism. Our proposed model may have potential applications in high-capacity optical communications and quantum information technologies.

Highly-excited Rydberg excitons in synthetic thin-film cuprous oxide

Cuprous oxide (hbox {Cu}{}_2hbox {O}) has recently emerged as a promising material in solid-state quantum technology, specifically for its excitonic Rydberg states characterized by large principal quantum numbers (n). The significant wavefunction size of these highly-excited states (proportional to n^2) enables strong long-range dipole-dipole (proportional to n^4) and van der Waals interactions (proportional to n^{11}). Currently, the highest-lying Rydberg states are found in naturally occurring hbox {Cu}_2hbox {O}. However, for technological applications, the ability to grow high-quality synthetic samples is essential. The fabrication of thin-film hbox {Cu}{}_2hbox {O} samples is of particular interest as they hold potential for observing extreme single-photon nonlinearities through the Rydberg blockade. Nevertheless, due to the susceptibility of high-lying states to charged impurities, growing synthetic samples of sufficient quality poses a substantial challenge. This study successfully demonstrates the CMOS-compatible synthesis of a hbox {Cu}{}_2hbox {O} thin film on a transparent substrate that showcases Rydberg excitons up to n = 8 which is readily suitable for photonic device fabrications. These findings mark a significant advancement towards the realization of scalable and on-chip integrable Rydberg quantum technologies.

Insight into light‐ and static‐electric‐field‐induced polarization on polaron‐pair dynamics in neat P3HT device: A transient‐absorption‐spectroscopy‐based study

AbstractWe have investigated the polaron‐pair dynamics following the excitation of vibrationally hot exciton states in organic semiconductor‐based optoelectronic devices to better understand the photophysical properties, which can help to improve the device performance. In our earlier work, published at ‘Phys. Chem. Chem. Phys., 2019,21, 21236‐21248’, we have investigated the role of the static electric internal and external fields on the polaron‐pair dynamics in a neat poly(3‐hexylthiophene‐2,5‐diyl) based device. From this, we have concluded that the polaron‐pair dissociates into charge carriers due to the internal field present inside the device and the dissociation process accelerates when an external electric field is also applied in reverse bias. Apart from the electric‐field‐induced dissociation process, we now have also been interested in the light‐ and electric‐field‐induced polarization effect on the polaron‐pair dynamics. For this, in the present study, we have used femtosecond transient absorption spectroscopy to investigate the polaron‐pair dynamics in a neat P3HT‐based device for different angles of incidence of the light with an additional variation of the static electric field. It is well‐known that thin‐film photovoltaics can be designed for improved angle‐dependent responsivity at specific angles and the photon harvesting efficiency depends on the incident angle of light. Internal electric fields together with the electric field of the incident light both influence the charge generation efficiency of the device, which is determined by the photophysical processes happening between electronic excitation and the formation of charge. The change of reflectivity due to the variation of incident angle and the effect of the electric‐field induced polarization make an overall impact on the polaron‐pair dynamics as demonstrated by our investigations.

Femtosecond Dynamics of Excited States of Chlorophyll Tetramer in Water-Soluble Chlorophyll-Binding Protein BoWSCP.

The paper reports on the absorption dynamics of chlorophyll a in a symmetric tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP. It was measured by a broadband femtosecond laser pump-probe spectroscopy within the range from 400 to 750 nm and with a time resolution of 20 fs-200 ps. When BoWSCP was excited in the region of the Soret band at a wavelength of 430 nm, nonradiative intramolecular conversion S3→S1 was observed with a characteristic time of 83 ± 9 fs. When the complex was excited in the region of the Qy band at 670 nm, relaxation transition between two excitonic states of the chlorophyll dimer was observed in the range of 105 ± 10 fs. Absorption spectra of the excited singlet states S1 and S3 of chlorophyll a were obtained. The delocalization of the excited state between exciton-coupled Chl molecules in BoWSCP tetramer changed in time and depended on the excitation energy. When BoWSCP is excited in the Soret band region, an ultrafast photochemical reaction is observed. This could result from the reduction of tryptophan in the vicinity of chlorophyll.

In English

Using a variational method within the framework of the effective mass approximation, using a triangular coordinate system of an electron, hole, and exciton moving in a titanium dioxide quantum dot, the exciton energy spectrum was obtained as a function of the radius a of the quantum dot. The variational wave function of the exciton contained factors that took into account the motion of an electron and a hole in a potential well of infinite depth of a quantum dot, as well as the form of a hydrogen-like wave function. It is shown that the occurrence of an exciton in a quantum dot has a threshold character. An exciton, as a bound state of an electron and a hole, is formed starting from a certain critical radius ac, the value of which exceeds the Bohr radius of the exciton in titanium dioxide. The exciton energy levels are located in the band gap of the titanium dioxide quantum dot. In this case, with an increase in the radius a of the quantum dot (so that a≥ac), a band of exciton states appears in the band gap of the titanium dioxide quantum dot. The mechanism for the formation of optical absorption spectra in nanosystems containing titanium dioxide nanocrystals are presented. It is found that the optical absorption of anatase NC, which was observed under the experimental conditions, was due to the appearance of an exciton in the NC. Using the variational calculation of the energy spectrum of an exciton in NC, the position of the absorption peak of NC anatase was determined. This absorption peak differs slightly from the absorption peak, which was obtained in the experimental work.

Efficient and stable green organic light-emitting diode utilizing an asymmetric butterfly-shaped chromophore with enhanced reverse intersystem crossing and suppressed exciton annihilation

Intermolecular electron-exchange interactions involving long-lived triplet state excitons dominate the quenching process of the films. In this work, a butterfly-shaped thermally activated delayed fluorescence (TADF) emitter 10,10′-(5-((3,5-di(9H-carbazol-9-yl)phenyl)sulfonyl)-1,3-phenylene)bis(9,9-dimethyl-9,10-dihydroacridine) (BCZ-DPS-BAD) with diphenylsulfone skeleton is constructed by modulating the rigid steric hindrance on the electron donor fragment to weaken intermolecular electron-exchange interactions. Analysis of the ground and excited state properties, crystal structure, steady-state and transient photophysical characteristics reveals that BCZ-DPS-BAD exhibits loose intermolecular arrangements with no direct facing close packing and weak π–π interactions of 4.18 Å and 4.67 Å. The triplet state excitons can swiftly return to the single exciton state in accordance with a short delayed fluorescence lifetime (2.3 μs) and a quick reverse intersystem crossing rate (1.85 × 106 s−1), obstructing the way for the triplet state to lose energy. A remarkable maximum external quantum efficiency of 21.8 %, maximum current efficiency of 56.8 cd/A and exciton utilization rate of 82 % is achieved for BCZ-DPS-BAD-based green non-doped OLED, concomitant with Commission Internationale d'Eclairage (CIE) coordinates of (0.30, 0.50). Notably, BCZ-DPS-BAD behaves stable non-doped OLED performance with efficiency roll-off of 4 % at 1000 cd m−2.

Waveguided phosphorescence through a gain medium by an in-plane pulsed laser stripe

Phosphorescent emissions at room temperature from solid-state self sustained film fabricated using phenazine derivative molecules blended in a solution of poly(methyl methacrylate) were investigated at steady-state experimental conditions. Stripe excitation by a pulsed laser at different levels of intensities and different lengths of stripes, originates a waveguided emission up to the edge of the film, enabling us to assume relatively higher gain characteristics for triplet state excitons. The analysis of the experimental results was done based on the relatively higher contribution of the total integrated area for the phosphorescent part of the emission spectra. The work opens an attainable procedure to enable future laser devices using phosphorescence at room temperature.

Ligand-Induced Symmetry Breaking as the Origin of Multiexponential Photoluminescence Decay in CdSe Quantum Dots.

The bright photoluminescence (PL) of colloidal CdSe quantum dots (QDs) makes them interesting for optical applications. For most of them, well-defined PL properties, dominated by a single excitonic state, are required. However, in many PL experiments with QD ensembles, multiexponential decay was observed. On the basis of spin-orbit density functional theory and screened configuration interaction calculations, we show that highly symmetric and defect-free CdSe QDs with diameters of 1.7 and 2.0 nm possess a multiexponential low-temperature PL at the single-dot level. This is a consequence of ligand-induced symmetry breaking with a subsequent rearrangement of the lowest eight excitonic states in two sets of four singly degenerate excitonic states. For each set, the lowest state is dark and the other three are bright. We find that the splitting between the sets can be modified by the coverage and choice of the ligand, which facilitates the engineering of the PL properties of CdSe QDs.

Exploring Highly Efficient Broadband Self-Trapped-Exciton Luminophors: from 0D to 3D Materials.

The review summarizes our recent reports on brightly-emitting materials with varied dimensionality (3D, 2D, 0D) synthesized using "green" chemistry and exhibiting highly efficient photoluminescence (PL) originating from self-trapped exciton (STE) states. The discussion starts with 0D emitters, in particular, ternary indium-based colloidal quantum dots, continues with 2D materials, focusing on single-layer polyheptazine carbon nitride, and further evolves to 3D luminophores, the latter exemplified by lead-free double halide perovskites. The review shows the broadband STE PL to be an inherent feature of many materials produced in mild conditions by "green" chemistry, outlining PL features general for these STE emitters and differences in their photophysical properties. The review is concluded with an outlook on the challenges in the field of STE PL emission and the most promising venues for future research.

Resonant optical reflection from a GaN/(Al,Ga)N excitonic Bragg structure

We experimentally demonstrate the formation of a superradiant optical mode in the room-temperature reflection spectra from a resonant Bragg structure composed of 30 equidistant GaN quantum wells separated by (Al,Ga)N barriers. The mode arises when the condition of the Bragg diffraction is fulfilled at the wavelength corresponding to the energy of the quasi-two-dimensional excitons in the quantum wells. It manifests itself as a significant increase in the amplitude and a change in the shape of the resonant optical reflection due to the electromagnetic coupling of the excitons. By modeling of the optical spectra, we evaluate the radiative and non-radiative broadening parameters of the excitonic states in the GaN quantum wells, which appear to be 0.4 ± 0.02 and 40 ± 5 meV, correspondingly, for the resonant exciton energy of 3.605 eV. The resonant Bragg structure based on the periodic sequence of the GaN quantum wells demonstrates an efficient coupling of photons and excitons at room temperature, which makes it promising for device applications.

Photoluminescence imaging of single photon emitters within nanoscale strain profiles in monolayer WSe2

Local deformation of atomically thin van der Waals materials provides a powerful approach to create site-controlled chip-compatible single-photon emitters (SPEs). However, the microscopic mechanisms underlying the formation of such strain-induced SPEs are still not fully clear, which hinders further efforts in their deterministic integration with nanophotonic structures for developing practical on-chip sources of quantum light. Here we investigate SPEs with single-photon purity up to 98% created in monolayer WSe2 via nanoindentation. Using photoluminescence imaging in combination with atomic force microscopy, we locate single-photon emitting sites on a deep sub-wavelength spatial scale and reconstruct the details of the surrounding local strain potential. The obtained results suggest that the origin of the observed single-photon emission is likely related to strain-induced spectral shift of dark excitonic states and their hybridization with localized states of individual defects.

Origin of Low-Lying Red States in the Lhca4 Light-Harvesting Complex of Photosystem I.

The antenna complexes of Photosystem I present low-lying states visible as red-shifted and broadened absorption and fluorescence bands. Among these, Lhca4 has the most evident features of these "red" states, with a fluorescence band shifted by more than 25 nm from typical LHC emission. This signal arises from a mixing of exciton and charge-transfer (CT) states within the excitonically coupled a603-a609 chlorophyll (Chl) dimer. Here we combine molecular dynamics, multiscale quantum chemical calculations, and spectral simulations to uncover the molecular mechanism for the formation and tuning of exciton-CT interactions in Lhca4. We show that the coupling between exciton and CT states is extremely sensitive to tiny variations in the Chl dimer arrangement, explaining both the red-shifted bands and the switch between conformations with blue and red emission observed in single-molecule spectroscopy. Finally, we show that mutating the axial ligand of a603 diminishes the exciton-CT coupling, removing any red-state fingerprint.

Conformational Effect on the Excitonic States of 2-Phenylpyridine Oligomers: Ab Initio Studies and Analysis.

In this work, we report the effect of different conformations of 2-phenylpyridine oligomers ((PhPy)n=1-5) on the excited state properties from the results obtained at the RI-ADC(2)/def2-TZVP level. Three different conformers, namely, A, B, and C, are considered for each oligomer. All the oligomers of conformer A have linear-type structures, whereas conformers B and C form helical structures at n = 5 and n = 3, respectively. The differences in the geometries of the three conformers are reflected in the UV and CD spectra. The UV spectra of conformer A show high-intensity peaks compared to the conformers B and C, for each oligomer. While the helical oligomers of conformers B and C show high-intensity CD bands, the intensities of CD bands for all of the oligomers of conformer A are weaker. Analysis of the properties of the first five excited states in (PhPy)5 is carried out using three descriptors, and the results reveal that these are partially charge transfer states.