Behavior Of Excitons Research Articles

The Rise of Colloidal Quantum Well Light‐Emitting Diodes

AbstractColloidal quantum wells (CQWs) recently become one of the most fascinating optoelectronics and microelectronics materials because of their outstanding properties, including ultranarrow emissions, high photoluminescence quantum efficiencies, and large exciton binding energies. Being a significant CQW application, CQW‐based light‐emitting diode (CQW‐LED) exhibits numerous merits such as extremely high color purity, high device efficiency, solution‐processable preparation, adjustable emission, and excellent compatibility with applied electronics. Herein, the progress of high‐performance CQW‐LEDs is insightfully reviewed, where the innovation of CQW materials as well as the optimization of device engineering are systematically summarized. First, the fundamental concepts in CQW‐LEDs are described, including how to realize CQW emitters, construct CQW‐LED architectures, and understand working mechanisms. Subsequently, various state‐of‐the‐art strategies for developing CQW‐LEDs are highlighted, where material optimizations, charge dynamics (e.g., charge injection, transport, and balance), and exciton behaviors (e.g., exciton generation and recombination) have an important effect on device performances. In the end, current challenges as well as future development opportunities are discussed. This work will present deep insights into achieving high‐performance CQW‐LEDs for next‐generation display, lighting, and optical communication technologies.

Delayed Fluorescence in Dual-Doped Perovskite Nanocrystals: Insight into the Role of Dopants.

This study investigates the photophysical behaviour of Mn/Fe and Mn/Sn co-doped CsPbCl3 perovskite nanocrystals (NCs) to explore carrier dynamics and dopant interactions. Using gated photoluminescence (PL) and temperature-dependent measurements, we elucidate the impact of dopant chemistry on exciton behaviour, focusing on vibrationally assisted delayed fluorescence (VADF) and energy transfer mechanisms. The efficiency of VADF is influenced by factors such as the bandgap, temperature, quantum confinement, and host composition. In Mn/Fe co-doped NCs, Fe-induced trap states introduce additional radiative pathways, resulting in a unique emission around 515 nm. In contrast, in Mn/Sn co-doped NCs, Sn captures photoexcited carriers, preventing the VADF process and leading to non-radiative decay. The findings provide key insights into dopant-dopant interactions and the mechanisms governing carrier transfer, enhancing our understanding of these materials for future optoelectronic applications.

Insights into excitonic behavior in single-atom covalent organic frameworks for efficient photo-Fenton-like pollutant degradation

The generation of radicals through photo-Fenton-like reactions demonstrates significant potential for remediating emerging organic contaminants (EOCs) in complex aqueous environments. However, the excitonic effect, induced by Coulomb interactions between photoexcited electrons and holes, reduces carrier utilization efficiency in these systems. In this study, we develop Cu single-atom-loaded covalent organic frameworks (CuSA/COFs) as models to modulate excitonic effects. Temperature-dependent photoluminescence and ultrafast transient absorption spectra reveal that incorporating acenaphthene units into the linker (CuSA/Ace-COF) significantly reduces exciton binding energy (Eb). This modification not only enhances peroxymonosulfate adsorption at Cu active sites but also facilitates rapid electron transfer and promotes selective hydroxyl radical generation. Compared to CuSA/Obq-COF (Eb = 25.6 meV), CuSA/Ace-COF (Eb = 12.2 meV) shows a 39.5-fold increase in the pseudo-first-order rate constant for sulfamethoxazole degradation (0.434 min−1). This work provides insights into modulating excitonic behavior in single-atom catalysts via linker engineering for EOCs degradation.

Polymerized Small‐Molecule Acceptors with Linker Length‐Dependent Photocatalytic Activity for High‐Performance Solar Hydrogen Evolution

AbstractDeveloping organic semiconductor photocatalysts with alterable optical properties and excitonic behaviors for photocatalytic hydrogen evolution has received significant attention recently. Herein, three polymerized small‐molecule acceptors (PSMAs) with different linker lengths, namely PY‐1T, PY‐2T and PY‐3T, are designed and synthesized to construct nano‐photocatalysts. In comparison with small‐molecule YDT, these PSMAs exhibit broader absorption in both visible and near‐infrared (NIR) light region as well as enlarged exciton diffusion length. In the meanwhile, the intramolecular charge transfer and separation in PSMAs is promoted by varying the linker length, leading to enhanced light harvesting and charge utilization. As a result, the single‐component nano‐photocatalyst based on PY‐3T achieves an impressive average hydrogen evolution rate (HER) of 400.3 mmol h−1 g−1 under AM 1.5G sunlight (100 mW cm−2), which is ≈48 times greater than that of YDT NPs (8.3 mmol g−1 h−1). These results not only prove the potential that developing polymerized small‐molecule acceptors with extended chain length as efficient photocatalysts, but also elucidate the importance of regulating linker length in designing high‐performance photocatalysts.

Cross-Transition-Dipole Stacking of Conjugated Organic Molecules: Structure, Exciton Behavior and Optoelectronic Property.

Organic conjugated molecules have gained widespread application as organic semiconductors due to their unique optoelectronic properties. The rigidity of these large conjugated structures facilitates strong intermolecular interactions, which significantly influence their properties in the solid state through various molecular arrangements. The study of the relationship among molecular arrangement, exciton behavior, and optoelectronic properties is an eternal research topic. Cross-dipole stacking is a specific molecular arrangement that demonstrates unique characteristics and has received continuous attention over the past decades. This mini-review will first discuss the unique exciton behaviors in cross-dipole stacking based on exciton models, including weak exciton coupling and suppression of Förster resonance energy transfer. These exciton behaviors, determined by molecular stacking arrangements, are fundamental to the optoelectronic properties of cross-dipole stacking systems. Next, we will introduce well-defined cross-dipole systems and summarize their design principles from a molecular structure perspective. Finally, we will present the specific optoelectronic properties of cross-dipole stacking systems and their outstanding performance, such as high solid-state luminescence, good charge carrier mobility, and significant CD/CPL. Through this mini-review, we hope to enhance the understanding of cross-dipole stacking, contributing to the construction of such systems, the exploration of excited-state behaviors, and the discovery of high-performance materials.

Novel exciton behavior in low-dimensional polarized MoSSe/GaN heterostructures: A first-principles study

Novel exciton behavior in low-dimensional polarized MoSSe/GaN heterostructures: A first-principles study

Spectroscopic Ellipsometry Study of the Temperature Dependences of the Optical and Exciton Properties of MoS2 and WS2 Monolayers.

The optical properties of MoS2 and WS2 monolayers are significantly influenced by fabrication methods, especially with respect to the behavior of excitons at the K-point of the Brillouin zone. Using spectroscopic ellipsometry, we obtain the complex dielectric functions of monolayers of these materials from cryogenic to room temperatures over the energy range 1.5 to 6.0 eV. The excitonic structure of each sample is analyzed meticulously by fitting the data to a standard analytical function to extract the energy positions of the excitons at each temperature. At low temperatures, excitonic structures are blue-shifted and sharpened due to the reduction in phonon noise and lattice distance. The excitons of monolayers fabricated by MOCVD separate into sub-structures at low temperatures, while monolayers grown by LPCVD and APCVD remain a single peak. The origin of these peaks as charged or neutral excitons follows from their temperature dependences.

Exciton dynamics in CsPbBr3 single crystal: LT splitting energy, exciton-polariton dispersion, and biexciton binding energy.

Metal halide perovskite materials (MHPs) are promising for several applications due to their exceptional properties. Understanding excitonic properties is essential for exploiting these materials. For this purpose, we focus on CsPbBr3 single crystals, which have higher crystal quality, are more stable, and have no Rashba effect at low temperatures compared to other 3D MHPs. We have estimated exciton energy positions, longitudinal-transverse splitting energy, and damping energy using low-temperature reflection spectra. Under high excitation intensity, two biexciton emissions (M-emission) and exciton-exciton scattering emission (P-emission) were observed. We assign the two M-emissions to the emission to the states of longitudinal and transverse excitons, i.e., ML and MT emissions. From the energy position of the MT emission, the biexciton binding energy has been estimated to be ∼2meV. By analyzing P-emission obtained from the back side of the sample, we have estimated the exciton binding energy to be 17.8-23.7meV. This estimation minimizes the influence of the wavenumber distribution in the scattering process. In addition, time-resolved transmittance measurements using pulsed white light have revealed the group velocity dispersion. Comparing experimental results with theoretical calculations using the Lorentz model clarifies that exciton dynamics in CsPbBr3 can be described with a simple Lorentz model. These insights enhance the understanding of exciton behavior and support the development of exciton-based devices using MHPs.

High‐Resolution X‐Ray Imaging With 0D Organic–Metal Halide Scintillator Featuring Reversed Exciton Trapping

AbstractScintillators, essential for applications in nuclear medicine, radiation detection, and industrial inspection, convert high‐energy radiation into visible light. Manganese (Mn)‐based inorganic–organic hybrid materials are distinguished by their thermal stability, mechanical strength, and flexibility. However, the effects of temperature on Mn(II)‐based hybrid scintillators have not been clearly analyzed, making the elucidation of their temperature‐dependent luminescence mechanisms particularly important. A notable advancement is the synthesis of Mn‐1 nanocrystals (NCs) using methyltriphenylphosphonium chloride (mtppCl) and MnCl₂. These NCs exhibit distinctive temperature‐dependent photoluminescence luminescence: the intensity decreases from 77 to 150 K but paradoxically increases at higher temperatures due to anomalous thermal exciton behavior in the [MnCl₄]2⁻ tetrahedra. Besides, Mn‐1 NCs achieve a detection limit of 1.01 µGyair/s, surpassing medical diagnostic standards and outperforming commercial scintillators such as Bi₄Ge₃O₁₂ (BGO). Additionally, they show exceptional stability under continuous irradiation and can be incorporated into a flexible scintillating film with a resolution of 11.3 lp/mm at an MTF of 0.2. The current study has further refined the luminescence mechanism of Mn(II)‐based materials and optimizes their properties for a wider range of applications.

Transient Optical Modulation in Vanadium and Selenium Doped MoS2 by Carrier–Carrier and Carrier–Phonon Interactions

AbstractDoping and alloying induce defect states in atomically thin transition metal dichalcogenides (TMDCs), leading to strong carrier–phonon interactions. The robust excitonic behavior of these layered materials can be modified by injecting a high density of charge carriers. However, comprehending the influence of carrier–phonon and carrier–carrier interactions on the optical properties of 2D materials is crucial for their optoelectronic and photonic applications. Here, transient absorption (TA) spectroscopy is employed to demonstrate the modulation of the transient optical behavior of TMDCs through doping and excitation near Mott density. The TA spectra reveal broadening attributed to carrier–carrier and carrier–phonon interactions, with the broadening being particularly pronounced in vanadium (V) doped TMDCs due to the hybridization of defect and exciton transitions. Analysis of TA kinetics suggests the involvement of various carrier species in the carrier dynamics of TMDCs, with the influence of mid‐gap carriers dominating at higher excitation densities. Nonetheless, the presence of strong carrier–phonon coupling in V‐doped TMDCs is demonstrated by temperature‐dependent Raman and photoluminescence spectroscopy. The results reveal that the enhanced coupling between acoustic phonons and carriers can lead to multiphonon emission. The findings of this study hold promise for controlling the optical response of TMDCs in ultrafast optoelectronic applications.

Recent progress in high-performance thermally activated delayed fluorescence exciplexes based on multiple reverse intersystem crossing channels

In the field of organic light-emitting diodes (OLEDs), exciplex materials with thermally activated delayed fluorescence (TADF) characteristics have garnered significant attention in recent years owing to their potential for high fluorescence efficiency, primarily achieved through the reverse intersystem crossing (RISC) process. By converting non-radiative triplet states to radiative singlet states, the RISC process can effectively regulate exciton behavior, resulting in the harvest of triplet excitons and the improvement of luminescence efficiency. Recently, multi-RISC strategies have been developed to further enhance the performance of TADF exciplex materials and devices. In this paper, we review these research progress in this area. We classify molecular design strategies according to the composition of exciplexes, discuss the design principles and energy-harvesting mechanism of high-performance TADF exciplexes based on multi-RISC strategies, and prospect their further research and development. The progressive endeavors summarized in this review may inspire further research on material design and device fabrication, and promote the development of OLED applications.

On-Off Switching of Singlet Self-Trapped Exciton Emission Endows Antimony-Doped Indium Halides with Excitation-Wavelength-Dependent Luminescence.

Excitation-wavelength-dependent (Ex-De) emitters are a fascinating category of luminescent materials whose emission properties vary with the wavelength of the light used for excitation. Antimony (Sb3+)-doped indium (In)-based metal halides are efficient light emitters; however, the peak fluorescence emission of most Sb3+-activated In-halide remains independent of the excitation wavelength. Here, the study introduces a new Sb3+-doped In-halide cluster, (BDPA)2InCl5:Sb (BDPA+ = C15H18N+, benzyldimethylphenylammonium), which demonstrates efficient Ex-De emission originating from the on-off switchable fluorescence behavior of singlet self-trapped exciton (STE) in 5-coordinate Sb3+ dopant. Interestingly, when excited within the range of 240-370nm, photoluminescence (PL) spectra of (BDPA)2InCl5:Sb show both singlet and triplet STE emission. However, under excitation wavelengths of 370 to 420nm, the singlet STE emission is absent, resulting in a noticeable correlated color temperature change from 1700 to 3800 K. The study provides a new approach to designing color-tunable Sb3+-based luminophores, and also presents a novel application scenario for the widely recognized Sb3+ doping strategy.

Multiconfigurational Excitonic Couplings in Homo- and Heterodimer Stacks of Azobenzene-Derived Dyes.

Molecular excitons play a major role within dye aggregates and hold significant potential for (opto)electronic and photovoltaic applications. Numerous studies have documented alterations in the spectral properties of dye homoaggregates, but only limited work has been reported for heteroaggregates. In this article, dimeric dye stacks were constructed from azobenzene-like dyes with identical or distinct structures, and their excitonic features were computationally investigated. Our results show that strong exciton coupling is not limited to identical chromophores, as often assumed, based on a recently made available Frenkel Exciton Hamiltonian and multiconfigurational plus second-order perturbation theory energetics methodology. Heteroaggregate stacks were found to exhibit different absorption features from the corresponding interacting monomers, indicating considerable coupling interactions between units. We analyzed how such coupling may vary according to various aspects, such as the relative positions of the interacting monomers or the differences in their energetics. Such qualitative and semiquantitative analyses allow the evaluation of the excitonic behavior of these dye aggregates to encourage further efforts toward a deeper understanding of the excitonic properties of tailored dye heteroaggregate systems.

Quantum tunneling high-speed nano-excitonic modulator

High-speed electrical control of nano-optoelectronic properties in two-dimensional semiconductors is a building block for the development of excitonic devices, allowing the seamless integration of nano-electronics and -photonics. Here, we demonstrate a high-speed electrical modulation of nanoscale exciton behaviors in a MoS2 monolayer at room temperature through a quantum tunneling nanoplasmonic cavity. Electrical control of tunneling electrons between Au tip and MoS2 monolayer facilitates the dynamic switching of neutral exciton- and trion-dominant states at the nanoscale. Through tip-induced spectroscopic analysis, we locally characterize the modified recombination dynamics, resulting in a significant change in the photoluminescence quantum yield. Furthermore, by obtaining a time-resolved second-order correlation function, we demonstrate that this electrically-driven nanoscale exciton-trion interconversion achieves a modulation frequency of up to 8 MHz. Our approach provides a versatile platform for dynamically manipulating nano-optoelectronic properties in the form of transformable excitonic quasiparticles, including valley polarization, recombination, and transport dynamics.

Robust excitonic light emission in 2D tin halide perovskites by weak excited state polaronic effect

2D perovskites hold immense promise in optoelectronics due to their strongly bound electron-hole pairs (i.e., excitons). While exciton polaron from interplay between exciton and lattice has been established in 2D lead-based perovskites, the exciton nature and behavior in the emerging 2D tin-based perovskites remains unclear. By combining spin-resolved ultrafast spectroscopy and sophisticated theoretical calculations, we reveal 2D tin-based perovskites as genuine excitonic semiconductors with weak polaronic screening effect and persistent Coulomb interaction, thanks to weak exciton-phonon coupling. We determine an excited state exciton binding energy of ~0.18 eV in n = 2 tin iodide perovskites, nearly twice of that in lead counterpart, despite of same large value of ~0.2 eV from steady state measurement. This finding emphasizes the pivotal role of excited state polaronic effect in these materials. The robust excitons in 2D tin-based perovskites exhibit excitation power-insensitive, high-efficiency and color-purity emission, rendering them superior for light-emitting applications.

Observation of anomalous excitonic emission in V-doped WS2 QDs synthesized by hydrothermal method and subsequent mechanical exfoliation

This study focuses on synthesizing vanadium (V) doped 2H phase WS2 via a facile hydrothermal method and subsequent liquid phase mechanical exfoliation of the material into QD-like nanostructures. An increment in dopant percentage from 1 % to 7 % red shifted the band gap of WS2 from 4.15 eV to 3.78 eV. The nanostructures show electronic transition due to B, A, and defect-bound excitons and demonstrate modulation of excitonic behavior with V doping. Low V doping provides the WS2 material with a reduced B/A excitonic peak intensity ratio because of the nonradiative pathways favoring the relaxation of high energy B excitons to A excitons. High V doping results in anomalous emission behavior marked by an increased B/A ratio, attributed to positive trion formation as a result of excess free hole concentration due to the p-type vanadium. The study suggests that V-doped WS2 nanostructures hold potential for technological applications, particularly in spintronics and photonics, emphasizing the importance of engineering exciton dynamics in two-dimensional materials using p-type substitutional dopants.

Optical properties of Cu2ZnSnS4 and Cu2CdSnS4 quaternary compounds

Nowadays, the efficiency of Cu2ZnSnS4 (CZTS) thin-film solar cells is still limited by various factors such as: electronic disorder, secondary phases and the presence of antisite defects. In order to avoid this limitations, the Zn substitution by heavier atoms like Cd was proposed, as it may inhibit the formation of antisite defects, thereby increasing the minority carrier lifetime and reducing electronic disorder in the system. Thus, the main goal of this work was to investigate the optical properties of Cu2ZnSnS4 (CZTS) and Cu2CdSnS4 (CCTS) quaternary compounds. Hence, the reflectance, transmittance and photoluminescence spectra were recorded over a wide temperature range (from 10 to 300 K). As a result, for the CZTS sample, the optical band gap energy at room temperature was found to be equal to 1.46 eV. Also, reflectance and photoluminescence spectra at 15 K revealed essential details about the excitonic behavior in the CCTS sample, in particular for the A type exciton, with ground and excited states (n A = 1 and n A = 2) observed. The binding energy for the A type exciton was found to be 64 meV, leading to an estimated band gap width (Eg) of about 1.39 eV. In addition, at higher energies, spectra revealed maxima associated with the ground and excited states (n B = 1 and n B = 2) of the B type exciton, with an estimated binding energy of 75 meV and a continuum energy of about 1.51 eV.

Manipulation of anisotropic Zhang-Rice exciton in NiPS3 by magnetic field

The effect of external magnetic fields on the behavior of the Zhang-Rice exciton in NiPS3, which captures the physics of spin-orbital entanglement in 2D XY-type antiferromagnets, remains unclear. This study presents systematic study of angle-resolved and polarization-resolved magneto-optical photoluminescence spectra of NiPS3 in the Voigt geometry. We observed highly anisotropic, non-linear Zeeman splitting and polarization rotation of the Zhang-Rice exciton, which depends on the direction and intensity of the magnetic field and can be attributed to the spin-orbital coupling and field-induced spin reorientation. Furthermore, above the critical magnetic field, we detected additional splitting of the exciton peaks, indicating the coexistence of various orientations of Néel vector. This study characterizes orbital change of Zhang-Rice exciton and field-induced spin-reorientation phase transitions in a 2D hexagonal XY-type antiferromagnet, and it further demonstrates the continuous manipulation of the spin and polarization of the Zhang-Rice exciton.

Understanding excitonic behavior and electroluminescence light emitting diode application of carbon dots

Carbon dots (CDs), due to their low cost, high stability, and high luminous efficiency, have emerged as an excellent material for the emissive layer in next-generation electroluminescent light-emitting diodes (ELEDs). However, improving the efficiency of fluorescent CDs-based ELEDs remains challenging, primarily because it is difficult to utilize triplet excitons in the electroluminescence process. Therefore, enhancing the exciton utilization efficiency of CDs during electroluminescence is crucial. Based on this, we exploited the characteristic large exciton binding energy commonly found in CDs to develop exciton-emitting CDs. These CDs facilitate the radiative recombination of excitons during electroluminescence, thereby improving the electroluminescent efficiency. By rationally selecting precursors, we developed high quantum efficiency CDs and subsequently constructed CDs-based ELEDs. The blue-light device exhibited an external quantum efficiency of over 4 %. This study introduces a novel design concept for CDs, providing a new strategy for developing high-performance blue ELEDs based on CDs.

On the optical characteristics of Cd-Doped gadolinium oxide: A DFT based theoretical study

This research investigated the optical characteristics of Cd-doped gadolinium oxide (Gd2O3) by employing density functional theory (DFT) along with the CASTEP simulation package. After the creation of a Gd2O3 supercell at an initial [2x1x1] scale, the study evaluated the altered properties of Gd2O3 at the supercell level to assess the impact of Cd-doping on the optical features of doped one. Optical properties which were explored included the examining the dielectric function, refractive index, conductivity, and loss function. The dielectric function exhibited distinct peaks at certain photon energies that corresponded to various electronic transitions between energy levels of the material. The prominent absorption peaks observed in the energy range of 0.174-1.55 eV in the imaginary part of the dielectric function. This was attributed to energy transitions occurring between specific orbitals for pure and Cd-doped gadolinium oxide. The refractive index exhibited stability at lower energy levels, while the conductivity curves displayed excitonic behavior in response to Cd-doping at the supercellular level. Furthermore, the Cd-doping resulted in an increase in absorption, as indicated by the simulated changes in the loss function