Stable Excitons Research Articles

Recent Progress of Organic Room‐Temperature Phosphorescent Hydrogels

Organic room‐temperature phosphorescent (RTP) materials have garnered significant attention owing to their unique photophysical properties. Traditionally, the stabilization of triplet excitons in RTP materials necessitates a crystalline matrix or rigid polymer chain, which limits their use in flexible materials. In contrast, hydrogels offer biocompatibility, softness, and ease of processing. Therefore, incorporating phosphorescent molecules into hydrogel systems can expand the application potential of RTP materials. This concept summarizes recent advancements in RTP hydrogels, emphasizing their synthetic strategies and diverse applications.

Ultralong room temperature phosphorescence with multicolor afterglow achieved in a harsh polymeric viscous flow state.

Polymer-based ultralong room temperature phosphorescence (RTP) is more attractive than that of organic small molecules. However, the intrinsic contradictions between the motion of the chain and the stability of phosphors' triplet excitons make achieving ultralong lifetime in polymeric systems a big challenge. Herein, we have achieved ultralong RTP emission in a polymeric viscous flow state with free chain motion through a facile B-O click reaction among boric acid, polyvinyl alcohol, and hydroxyl silicone oil. The yielded RTP putties (RTPPs) exhibited long lifetimes under ambient conditions (up to 2.39 s), surpassing those of all reported elastic RTP polymers and most glassy RTP polymers. Furthermore, multi-color afterglow can be achieved in RTPPs using the triplet-to-singlet Förster resonance energy transfer strategy. Impressively, utilizing viscous liquid features combined with RTP performance, RTPPs can be easily applied in complex models, handiwork, and anti-counterfeiting. Therefore, this progress, achieving a long phosphorescence lifetime in a viscous flow state, greatly expands the application scope of polymeric RTP materials and further compels a conceptual advance of polymeric RTP.

Polarization-Controlled Exciton-Polaritons in WS2 Strongly Coupled with Low-Symmetry Photonic Crystal Nanostructures.

Atomically thin transition metal dichalcogenides (TMDs) with ambient stable exciton resonances have emerged as an ideal material platform for exciton-polaritons. In particular, the strong coupling between excitons in TMDs and optical resonances in anisotropic photonic nanostructures can form exciton-polaritons with polarization selectivity, which offers a new degree of freedom for the manipulation of the light-matter interaction. In this work, we present the experimental demonstration of polarization-controlled exciton-polaritons in tungsten disulfide (WS2) strongly coupled with polarization singularities in the momentum space of low-symmetry photonic crystal (PhC) nanostructures. The utilization of polarization singularities can not only effectively modulate the polarization states of exciton-polaritons in the momentum space but also facilitate or suppress their far field coupling capabilities by tuning the in-plane momentum. Our results provide new strategies for creating polarization-selective exciton-polaritons.

Spin-Flip-Restricted Multiple-Resonance Emitters for Extended Device Lifetime in Indolocarbazole-Based Blue Organic Light-Emitting Diodes.

In this study, a multiple-resonance (MR) core structure is developed with a spin-flip-restricted emission mechanism based on a fused indolo[3,2,1-jk]carbazole (ICz) framework as emitters to improve the lifetime of blue organic light-emitting diodes. The molecular skeleton modulation approach applied to the conjugated π-system effectively stabilizes the triplet energy of the fused ICz emitters and narrows the full-width-at-half maximum (<20nm). In addition, the emitters exhibit higher exciton stability than conventional boron-based MR emitters. The fused ICz-based blue fluorescent device exhibits a high external quantum efficiency of 7.2%, a blue index of 68.6cd A-1 at a Commission internationale de l'éclairage y coordinate (CIEy) of 0.075, and a device lifetime 1.8 times longer than that of a boron-based emitter. In addition, a phosphor-sensitized fluorescent device based on the ICz emitter exhibited an improved external quantum efficiency of 20.6% with a CIEy coordinate of 0.076.

(Invited) Blue Organic Light-Emitting Diode Using Dynamic Exciton for Low Driving Voltage

Among the three primary colors, blue emission in organic light-emitting diodes (OLEDs) are highly important but very difficult to develop. OLEDs have already been commercialized; however, blue OLEDs have the problem of requiring a high applied voltage due to the high-energy of blue emission. Herein, an ultralow voltage turn-on at 1.47 V for blue emission with a peak wavelength at 462 nm (2.68 eV) is demonstrated in an OLED device. This OLED reaches 100 cd/m2, which is equivalent to the luminance of a typical commercial display, at 1.97 V. Blue emission from the OLED is achieved by the selective excitation of the low-energy triplet states at a low applied voltage by using the charge transfer (CT) state as a precursor and the triplet-triplet annihilation, which forms one emissive singlet from two triplet excitons. We found that the essential component for efficient blue emission is a smaller energy difference between the CT state and triplet exciton, accelerating the energy transfer between the two states and achieving the optimal performance by avoiding direct decay from the CT state to the ground state. Our study demonstrates that the developed OLED allows for a much longer operation lifetime than that from a typical blue phosphorescent OLED because the blue emission originates from a stable low-energy triplet exciton that avoids degrading the constituent materials.

Ligand compensation enabling efficient and stable exciton recombination in perovskite QDs for high-performance QLEDs

Ligand compensation enabling efficient and stable exciton recombination in perovskite QDs for high-performance QLEDs

Chiral Polymer‐Organic Molecule Composite with Circularly Polarized Thermally Activated Delayed Fluorescence and Room‐Temperature Phosphorescence by Bridging Effect of Hydrogen Bond

AbstractCircularly polarized luminescence is essential to chiral and photonic science, but achieving circularly polarized thermally activated delayed fluorescence (CP‐TADF) and circularly polarized room‐temperature phosphorescence (CP‐RTP) simultaneously remains a great challenge. This is because it is difficult to satisfy simultaneously the stable triplet exciton, appropriate energy gap, and the regular chiral environment. Herein, a simple strategy is reported to construct a persistent photoluminescent system, which can achieve TADF and RTP simultaneously by suppressing the non‐radiative transition decay of the triplet exciton through intermolecular hydrogen bonding between acridine flavin (AF) and rigid polymer network. The persistent photoluminescent composite exhibited ultra‐long lifetimes and high quantum yields. Then, a rarely multi‐circularly polarized photoluminescence system containing CP‐TADF and CP‐RTP is constructed by the co‐assembly of cellulose nanocrystals, polyvinyl alcohol, and AF. By utilizing the cholesteric structure, photonic band gap of chiral photonic crystals, and the stabilization mechanism of triplet exciton by intermolecular hydrogen bonding between the light emitter and rigid polymer, chiral photoluminescent films exhibited rare optical properties simultaneously: multi‐circularly polarized photoluminescence emission, high and tunable dissymmetric factor, significant quantum yield, and ultralong lifetimes, which are not reported before and broaden the perspective for multi‐circularly polarized luminescence.

Tunable multicolor-emission in Eu3+ and Tb3+ codoped Cs2NaInCl6:Sb3+ double perovskite nanocrystals and its dual-model anti-counterfeiting and temperature-sensing applications

Lead-free metal halide double perovskites with non-toxicity and stable self-trapped excitons (STEs) have received considerable attention in the field of photoelectric applications. However, it is difficult to achieve independent control of its photoluminescence performance to meet the requirements of multi-band emission. Herein, a doping strategy was employed to introduce lanthanide ions (Ln3+) into Cs2NaInCl6:Sb3+ nanocrystals (NCs), enabling the multicolor emission modulation ranging from blue to red and even white light. Benefiting from the efficient energy transfer from Sb-related self-trapped excitons to Ln3+ ions, green and red emissions originate from the 5D0→7FJ (J = 1, 2, 3, 4) transition of Eu3+ ions and 5D4-7FJ (J = 6, 5, 4, 3) transition of Tb3+ ions, respectively. According to the tunable polychromatic photoluminescence characteristics of doped NCs, the dual-mode fluorescent anti-counterfeiting applications were exhibited. Furthermore, the distinct temperature sensitivities exhibited by blue (453 nm) and red (617 nm) emission in Cs2NaInCl6:Sb3+/Eu3+ NCs provide the opportunity for the optical thermometry, which demonstrates the maximum absolute and relative sensitivity are 0.0018 and 0.43 % K−1, respectively. These results indicate that the synthesized codoped NCs have the potential applications in multifunctional fields, such as optical thermometer, fluorescence anti-counterfeiting, and multicolor-LEDs.

Achieving High-Temperature Phosphorescence by Organic Cocrystal Engineering.

Organic phosphors offer a promising alternative in optoelectronics, but their temperature-sensitive feature has restricted their applications in high-temperature scenarios, and the attainment of high-temperature phosphorescence (HTP) is still challenging. Herein, a series of organic cocrystal phosphors are constructed by supramolecular assembly with an ultralong emission lifetime of up to 2.16 s. Intriguingly, remarkable stabilization of triplet excitons can also be realized at elevated temperature, and green phosphorescence is still exhibited in solid state even up to 150 °C. From special molecular packing within the crystal lattice, it has been observed that the orientation of isolated water cluster and well-controlled molecular organization via multiple interactions can favor the structural rigidity of cocrystals more effectively to suppress the nonradiative transition, thus resulting in efficient room-temperature phosphorescence and unprecedented survival of HTP.

Achieving High‐Temperature Phosphorescence by Organic Cocrystal Engineering

AbstractOrganic phosphors offer a promising alternative in optoelectronics, but their temperature‐sensitive feature has restricted their applications in high‐temperature scenarios, and the attainment of high‐temperature phosphorescence (HTP) is still challenging. Herein, a series of organic cocrystal phosphors are constructed by supramolecular assembly with an ultralong emission lifetime of up to 2.16 s. Intriguingly, remarkable stabilization of triplet excitons can also be realized at elevated temperature, and green phosphorescence is still exhibited in solid state even up to 150 °C. From special molecular packing within the crystal lattice, it has been observed that the orientation of isolated water cluster and well‐controlled molecular organization via multiple interactions can favor the structural rigidity of cocrystals more effectively to suppress the nonradiative transition, thus resulting in efficient room‐temperature phosphorescence and unprecedented survival of HTP.

Targeting Compact and Ordered Emitters by Supramolecular Dynamic Interactions for High-performance Organic Ambient Phosphorescence.

Purely organic room-temperature phosphorescence (RTP) materials have received intense attention due to their fascinating optical properties and advanced optoelectronic applications. The promotion of intersystem crossing (ISC) and minimalization of nonradiative dissipation under ambient conditions are key prerequisites for realizing high-performance organic RTP; However, the ISC process is generally inefficient for organic fluorogens and the populated triplet excitons are always too susceptible to be well stabilized by conventional means. Particularly, organizing organic fluorophores into compact and ordered entities by supramolecular dynamic interactions has proven to be a newly-emerged strategy to boost the ISC process greatly and suppress the non-radiative relaxations immensely, facilitating the population and stabilization of triplet excitons to access high-performance organic RTP. Consequently, well-defined organic emitters enable robust RTP emission even in the solution state, thus greatly extending the applications. Here, this review is focused on a timely and brief introduction to recent progress in tailoring ordered high-performance RTP emitters by supramolecular dynamic interactions. Their typical preparation strategies, optoelectronic properties, and applications are thoroughly summarized. In the summary section, key challenges and perspectives of this field are highlighted to suggest potential directions for future study.

Unmasking the Electrochemiluminescence Properties of Ternary Mn/Fe/Co Metals Doped Porous g-C3N4 Fiber-like Nanostructure.

Graphitic-phase carbon nitride (g-C3N4) materials have exhibited increasingly remarkable performance as emerging electrochemiluminescence (ECL) emitters, owing to their unique optical and electronic properties; however, the ECL merits of porous g-C3N4 nanofibers doped with ternary metals are not yet explored. Deciphering the ECL properties of trimetal-doped g-C3N4 nanofibers could provide an exquisite pathway for ultrasensitive sensing and imaging with impressive advantages of minimal background signal, great sensitivity, and durability. Herein, we rationally synthesized g-C3N4 nanofibers doped atomically with Mn, Fe, and Co elements (Mn/Fe/Co/g-C3N4) in a one-pot via the protonation in ethanol and annealing process driven by the rolling up mechanism. The ECL performance of g-C3N4 with and without metal dopants was investigated and compared with standard Ru(bpy)32+ in the presence of potassium persulfate (K2S2O8) as the coreactant. Notably, g-C3N4 nanofibers doped with metal ions exhibited an ECL efficiency of 483% that was 4.83 times higher than that of Ru(bpy)32+. Mechanistic investigations unveiled that the g-C3N4 nanofibers possess a large surface area and, as a result, exhibit a reduced interfacial impedance within the porous microstructure. These factors contribute to the acceleration of charge transfer rates and the stabilization of charge carriers and excitons, ultimately facilitating the ECL process. This research endeavor may pave the way for a new hot research area and serves as a powerful tool for elucidating fundamental inquiries of ECL on one-dimensional g-C3N4 nanostructures.

Monolayer-like Exciton Recombination Dynamics of Multilayer MoSe2 Observed by Pump-Probe Microscopy.

Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.g., >10 layers) flakes is still absent. Recent computational studies have suggested that excitons in bulk TMDCs are confined to individual layers, leading to room-temperature stable exciton populations. Using this new context, we explore the carrier dynamics in MoSe2 flakes that are between ∼16 and ∼125 layers thick. We assign the kinetics to exciton-exciton annihilation (EEA) and Shockley-Read-Hall recombination of free carriers. Interestingly, the average observed EEA rate constant (0.003 cm2/s) is nearly independent of flake thickness and 2 orders of magnitude smaller than that of an unencapsulated monolayer (0.33 cm2/s) but very similar to values observed in encapsulated monolayers. Thus, we posit that strong intralayer interactions minimize the effect of layer thickness on recombination dynamics, causing the multilayer to behave like the monolayer and exhibit an apparent EEA rate intrinsic to MoSe2.

High-efficiency color-tunable ultralong room-temperature phosphorescence from organic-inorganic metal halides via synergistic inter/intramolecular interactions.

Materials exhibiting highly efficient, ultralong and multicolor-tunable room-temperature phosphorescence (RTP) are of practical importance for emerging applications. However, these are still very scarce and remain a formidable challenge. Herein, using precise structure design, several novel organic-inorganic metal-halide hybrids with efficient and ultralong RTP have been developed based on an identical organic cation (A). The original organic salt (ACl) exhibits red RTP properties with low phosphorescence efficiency. However, after embedding metals into the organic salt, the changed crystal structure endows the resultant metal-halide hybrids with excellent RTP properties. In particular, A2ZnCl4·H2O exhibits the highest RTP efficiency of up to 56.56% with a long lifetime of up to 159 ms. It is found that multiple inter/intramolecular interactions and the strong heavy-atom effect of the rigid metal-halide hybrids can suppress molecular motion and promote the ISC process, resulting in highly stable and localized triplet excitons followed by highly efficient RTP. More crucially, multicolor-tunable fluorescence and RTP achieved by tuning the metal and halogen endow these materials with wide application prospects in the fields of multilevel information encryption and dynamic optical data storage. The findings promote the development of phosphorescent metal-halide hybrids for potential high-tech applications.

Near-Unity Emitting, Widely Tailorable, and Stable Exciton Concentrators Built from Doubly Gradient 2D Semiconductor Nanoplatelets.

The strength of electrostatic interactions (EIs) between electrons and holes within semiconductor nanocrystals profoundly affects the performance of their optoelectronic systems, and different optoelectronic devices demand distinct EI strength of the active medium. However, achieving a broad range and fine-tuning of the EI strength for specific optoelectronic applications is a daunting challenge, especially in quasi two-dimensional core-shell semiconductor nanoplatelets (NPLs), as the epitaxial growth of the inorganic shell along the direction of the thickness that solely contributes to the quantum confined effect significantly undermines the strength of the EI. Herein we propose and demonstrate a doubly gradient (DG) core-shell architecture of semiconductor NPLs for on-demand tailoring of the EI strength by controlling the localized exciton concentration via in-plane architectural modulation, demonstrated by a wide tuning of radiative recombination rate and exciton binding energy. Moreover, these exciton-concentration-engineered DG NPLs also exhibit a near-unity quantum yield, high photo- and thermal stability, and considerably suppressed self-absorption. As proof-of-concept demonstrations, highly efficient color converters and high-performance light-emitting diodes (external quantum efficiency: 16.9%, maximum luminance: 43,000 cd/m2) have been achieved based on the DG NPLs. This work thus provides insights into the development of high-performance colloidal optoelectronic device applications.

Synthesis of highly efficient novel two-step spatial 2D photocatalyst material WS2/ZnIn2S4 for degradation/reduction of various toxic pollutants

In this article, we report the synthesis, characterization of novel biofriendly 2D/2D heterostructure WS2/ZnIn2S4 material in which 2D WS2 nanosheets are uniformly distributed spatially onto the spherically arranged 2D leaves of ZnIn2S4. We then studied the in-depth photocatalytic degradation activity of this novel nanocomposite and its pristine component materials on cationic dye: malachite green, anionic dye: congo red and reduction of heavy metal: chromium(VI) and the degradation efficiency of composite material was also tested on rhodamine-B, methylene blue, methyl orange dyes and acetaminophen/paracetamol drug. Form factor, structure factor and shape factor analysis has been carried out using X-ray diffractometry (XRD). Bond vibrations, functional groups and phonon vibration mode analysis has been done based on Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. Morphological and compositional analysis has been done using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDAX) and X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM). Surface area and pore size/distribution was characterized using Brunauer–Emmett–Teller (BET) method and Barrett-Joyner-Halenda Model. Degradation pathways and intermediate products are proposed using the high-performance liquid chromatography (HPLC). Photocatalytic activity of the nanocomposite WS2/ZnIn2S4 is compared with pristine ZnIn2S4 and pristine WS2, which shows more than 50% enhancement in both efficiency and rate of degradation/reduction for all the pollutants. A scavenger study was carried out to get insight of primary and secondary reactive oxygen species (ROS) taking part in degradation. Exciton lifetime, surface charge and stability, and flat band positions were studied based on time-correlated single photon counting (TCSPC) also known as time-resolved photoluminescence (TRPL), zeta potential, and Mott-Schottky respectively. Rate kinetics study was performed to analyze the physical and chemical behaviour of the nanocomposite with pollutants in consideration. Results show ∼100%, ∼90%, and ∼95% degradation efficiency by the heterostructure for malachite green (MG), congo red (CR), and reduction of heavy metal chromium (Cr(VI)) respectively within 5 min, which is a huge improvement as compared to pristine WS2 and pristine ZnIn2S4, both of which show the efficiencies of only ∼25% to∼75% in all the cases.

Construction of room temperature phosphorescent materials with ultralong lifetime by in-situ derivation strategy

Although room temperature phosphorescence (RTP) materials have been widely investigated, it is still a great challenge to improve the performance of RTP materials by promoting triplet exciton generation and stabilization. In this study, an in-situ derivation strategy was proposed to construct efficient RTP materials by in-situ deriving guest molecules and forming a rigid matrix during co-pyrolysis of guest molecules and urea. Characterizations and theoretical calculations revealed that the generated derivatives were beneficial for promoting intersystem crossing (ISC) to produce more triplet excitons, while rigid matrix could effectively suppress the non-radiative transition of triplet excitons. Thus, the in-situ derivation strategy was concluded to simultaneously promote the generation and stabilization of triplet excitons. With this method, the ultralong lifetime of RTP materials could reach up to 5.33 s and polychromatic RTP materials were easily achieved. Moreover, the potential applications of the RTP materials in reprocessing or editable anti-counterfeiting were successfully demonstrated.

Single-Exciton Photoluminescence in a GaN Monolayer inside an AlN Nanocolumn.

GaN/AlN heterostructures with thicknesses of one monolayer (ML) are currently considered to be the most promising material for creating UVC light-emitting devices. A unique functional property of these atomically thin quantum wells (QWs) is their ability to maintain stable excitons, resulting in a particularly high radiation yield at room temperature. However, the intrinsic properties of these excitons are substantially masked by the inhomogeneous broadening caused, in particular, by fluctuations in the QWs' thicknesses. In this work, to reduce this effect, we fabricated cylindrical nanocolumns of 50 to 5000 nm in diameter using GaN/AlN single QW heterostructures grown via molecular beam epitaxy while using photolithography with a combination of wet and reactive ion etching. Photoluminescence measurements in an ultrasmall QW region enclosed in a nanocolumn revealed that narrow lines of individual excitons were localized on potential fluctuations attributed to 2-3-monolayer-high GaN clusters, which appear in QWs with an average thickness of 1 ML. The kinetics of luminescence with increasing temperature is determined via the change in the population of localized exciton states. At low temperatures, spin-forbidden dark excitons with lifetimes of ~40 ns predominate, while at temperatures elevated above 120 K, the overlying bright exciton states with much faster recombination dynamics determine the emission.

Exciton dissociation in 2D layered metal-halide perovskites

Layered 2D perovskites are making inroads as materials for photovoltaics and light emitting diodes, but their photophysics is still lively debated. Although their large exciton binding energies should hinder charge separation, significant evidence has been uncovered for an abundance of free carriers among optical excitations. Several explanations have been proposed, like exciton dissociation at grain boundaries or polaron formation, without clarifying yet if excitons form and then dissociate, or if the formation is prevented by competing relaxation processes. Here we address exciton stability in layered Ruddlesden-Popper PEA2PbI4 (PEA stands for phenethylammonium) both in form of thin film and single crystal, by resonant injection of cold excitons, whose dissociation is then probed with femtosecond differential transmission. We show the intrinsic nature of exciton dissociation in 2D layered perovskites, demonstrating that both 2D and 3D perovskites are free carrier semiconductors and their photophysics is described by a unique and universal framework.

Inorganic salt recrystallization strategy for achieving ultralong room temperature phosphorescence through structural confinement and aluminized reconstruction

Achieving highly efficient and stable room temperature phosphorescence (RTP) with ultralong lifetime is critical for the multi-purpose applications of phosphorescent materials. In this work, we propose an inorganic salt heating recrystallization strategy to simultaneously improve the lifetime, quantum efficiency, and stability of phosphorescent scandium/leucine microspheres (Sc/Leu-MSs). Inorganic salt-treated Sc/Leu-MSs are obtained by simply heating and drying inorganic salt solution containing Sc/Leu-MSs, which can achieve a maximum lifetime increase of 4.42-times from 208.37 ms (Sc/Leu-MSs) to 920.08 ms (Al2(SO4)3-treated Sc/Leu-MSs), accompanied by a RTP intensity increase up to 24.08-times. The enhancement mechanism of RTP efficiency is attributed to the stabilization of triplet excitons caused by inorganic salt coating that suppresses molecular motion and isolates oxygen on the one hand, and the efficient intersystem crossing promoted by aluminized reconstruction-caused duplex heavy atom effects on the other hand. This study provides new design principle and a facile strategy to construct RTP materials with ultralong lifetime, high phosphorescent quantum efficiency, and high stability for promising applications such as anti-counterfeiting and light emitting diodes.