Exciton Dynamics Research Articles

Enhanced Förster Energy Transfer Through Horizontal Orientation of Sensitizer Molecules in Hyperfluorescent Organic Light‐Emitting Diodes

AbstractFörster resonance energy transfer (FRET) in sensitized fluorescent (SF) organic light‐emitting diodes (OLEDs) is an important process for suppressing triplet exciton loss during energy transfer toward the fluorescent dopant. Herein, the contribution of the relative orientation between the sensitizer and emitting dopant to the FRET in state‐of‐the‐art SF OLEDs is explained using experimental and theoretical approaches. The enhanced relative orientation factor (κ2) from 0.375 to 1.250 is theoretically demonstrated in the FRET theory depending on the orientation of the sensitizer and emitting dopant. On comparing two SF OLED systems with different sensitizers, the sensitizer with a higher horizontal dipole orientation exhibits a higher FRET rate, resulting in the enhanced κ2. The exciton dynamics under device operation are explored to quantitatively verify the contribution of the enhanced FRET rate to the exciton transfer processes; the triplet consumption rate of the sensitizer improves by 2.2 times, demonstrating an efficient exciton transfer.

Effect of Hydrogen Bonding on Thermally Activated Delayed Fluorescence Behaviors Based on a Study of Hydrate Crystals.

Reverse intersystem crossing (RISC) in purely organic molecules has become an attractive research topic since the demonstration of high efficiencies in organic light-emitting diodes using thermally activated delayed fluorescence (TADF). Although the intermolecular interactions have a significant impact on the exciton dynamics, it is generally difficult to identify the quantitative relationship associated with a specific factor. In this work, we used a clathrate crystal with TADF and H2O molecules to evaluate the effect of hydrogen bonding while maintaining molecular conformations and other intermolecular interactions. The hydrogen bonding shifted the charge transfer excited states to lower energies, resulting in superior TADF properties. Although the increase in the RISC rate is considered to enhance the stabilities of TADF molecules, photostability analysis revealed nearly the same degradation speed despite the 3 times faster RISC rate.

P‐105: Understanding Recombination Dynamics from Electroluminescence of Organic Light‐Emitting Diodes Using Artificial Intelligence

Distinguishing exciton and polaron dynamics in the electroluminescence (EL) of organic light‐emitting diodes (OLEDs) is difficult since the delayed EL originated from a combination of the excitonic process and slow recombination process. In this work, the recombination dynamics was extracted from the transient EL only via prediction of the recombination coefficient using artificial intelligence (AI). AI model with a high prediction accuracy (R 2 ) of 0.947 successfully analyzed the polaron dynamics of exciplex‐forming co‐host‐based OLEDs.

Exciton Dissociation, Charge Transfer, and Exciton Trapping at the MoS2/Organic Semiconductor Interface

Hybrid inorganic–organic semiconducting devices consisting of monolayer transition metal dichalcogenides (TMDs) represent a new frontier in advanced optoelectronics due to their high radiative efficiencies and capacity to form flexible p–n junctions with inherent device tunability. However, understanding how excitons and charges behave at the interface between TMDs and organic systems, a key requirement to advance the field, remains underexplored. Herein, a heterostructure consisting of a highly conjugated organic system, 9-(2-naphthyl)-10-[4-(1-naphthyl)phenyl]anthracene (ANNP), and monolayer molybdenum disulfide (MoS2) on quartz is elucidated via transient absorption and photoluminescence spectroscopies. Upon direct excitation of MoS2 at 532 nm, hole transfer to ANNP of ∼5 ps and a charge separation time constant of ∼2.4 ns are observed. When the sample is excited at 400 nm (where both ANNP and MoS2 absorb), a self-trapped exciton within ANNP is formed. The emission of the self-trapped exciton is long-lived compared to the exciton lifetime of ANNP, decaying within 20 ns. The trapping of the ANNP exciton is caused by structural deformities of the ANNP crystal lattice when grown on MoS2, which are removed by annealing the film. These observations highlight how exciton dissociation and charge transfer dominate at the interface of ANNP and MoS2 whereas the exciton dynamics within ANNP are prone to the formation of trap states brought about by crystal defects within the film. These insights will aid in future developments of TMD-containing optoelectronics.

Charge Carrier Localization Impact on the Spectral–Temporal Photoluminescence Separation in Type II CdTe/CdSe Nano-Heterostructures

Peculiarities of exciton dynamics in tetrapod-shaped CdTe/CdSe nanocrystals (nanotetrapods) are revealed under various optical excitation conditions. The photoluminescence (PL) spectra exhibit a pair of well resolved excitonic bands originating from CdTe and CdSe parts of the tetrapod arms as well as PL caused by the indirect transitions of spatially separated charge carriers (CT band). We demonstrate the pump intensity dependent giant blue shift of the indirect transition emission band caused by the exciton’s space filling effect and the modification of energy level structure by the induced internal electric field in both domains. The first-principles calculations reveal that the ground states of both electrons and holes are localized in the CdSe domain, but the charge carrier spatial separation is still present, as holes are localized at the interface. This picture is proven by the time-resolved PL measurements from the sub-picoseconds to tens of nanoseconds range, which demonstrate the presence of a picosecond time scale corresponding to the indirect excitons being much smaller than the previously observed value.

Photophysical dynamics of excitons in polyaniline nanotubes with enhanced resistance against exciton quenching for applications in flexible high-efficiency PLEDs

The development of a high-efficiency polymer light-emitting diode is strongly hindered by injected charge carriers in the emissive polymer layer. But real-time identification of the interactions that quench the photoluminescence is extremely difficult owing to the complex photophysics of polymers involved in it. Here, we have synthesized the polyaniline nanotubes to study interactions at the nanoscale within the emissive layer. Acid doping of PAni helped us to quantify the processes that suppress the emission, e.g., Förster resonance energy transfer (FRET) and charge transfer (CT). We have developed a material design perspective by demonstrating how an effective increase in conjugation length of PAni nanochain through 1D nanostructure growth can avoid the undesired emission quenching due to exciton quenching by the polarons. We have demonstrated how this approach helped us to preserve up to 95 % of the emission, which would otherwise be lost by exciton-polaron quenching interaction. Exploration of this new strategy could be a way forward for both fundamental and application aspects to enhance the emission efficiency of the conducting conjugate polymers and emissive layers in flexible polymer light-emitting diodes (PLEDs).

Multimodal Biofilm Inactivation Using a Photocatalytic Bismuth Perovskite-TiO2-Ru(II)polypyridyl-Based Multisite Heterojunction.

Infectious bacterial biofilms are recalcitrant to most antibiotics compared to their planktonic version, and the lack of appropriate therapeutic strategies for mitigating them poses a serious threat to clinical treatment. A ternary heterojunction material derived from a Bi-based perovskite-TiO2 hybrid and a [Ru(2,2'-bpy)2(4,4'-dicarboxy-2,2'-bpy)]2+ (2,2'-bpy, 2,2'-bipyridyl) as a photosensitizer (RuPS) is developed. This hybrid material is found to be capable of generating reactive oxygen species (ROS)/reactive nitrogen species (RNS) upon solar light irradiation. The aligned band edges and effective exciton dynamics between multisite heterojunctions are established by steady-state/time-resolved optical and other spectroscopic studies. Proposed mechanistic pathways for the photocatalytic generation of ROS/RNS are rationalized based on a cascade-redox processes arising from three catalytic centers. These ROS/RNS are utilized to demonstrate a proof-of-concept in treating two elusive bacterial biofilms while maintaining a high level of biocompatibility (IC50 > 1 mg/mL). The in situ generation of radical species (ROS/RNS) upon photoirradiation is established with EPR spectroscopic measurements and colorimetric assays. Experimental results showed improved efficacy toward biofilm inactivation of the ternary heterojunction material as compared to their individual/binary counterparts under solar light irradiation. The multisite heterojunction formation helped with better exciton delocalization for an efficient catalytic biofilm inactivation. This was rationalized based on the favorable exciton dissociation followed by the onset of multiple oxidation and reduction sites in the ternary heterojunction. This together with exceptional photoelectric features of lead-free halide perovskites outlines a proof-of-principle demonstration in biomedical optoelectronics addressing multimodal antibiofilm/antimicrobial modality.

Solution-Processed NiPS3 Thin Films from Liquid Exfoliated Inks with Long-Lived Spin-Entangled Excitons.

Antiferromagnets are promising materials for future opto-spintronic applications since they show spin dynamics in the THz range and no net magnetization. Recently, layered van der Waals (vdW) antiferromagnets have been reported, which combine low-dimensional excitonic properties with complex spin-structure. While various methods for the fabrication of vdW 2D crystals exist, formation of large area and continuous thin films is challenging because of either limited scalability, synthetic complexity, or low opto-spintronic quality of the final material. Here, we fabricate centimeter-scale thin films of the van der Waals 2D antiferromagnetic material NiPS3, which we prepare using a crystal ink made from liquid phase exfoliation (LPE). We perform statistical atomic force microscopy (AFM) and scanning electron microscopy (SEM) to characterize and control the lateral size and number of layers through this ink-based fabrication. Using ultrafast optical spectroscopy at cryogenic temperatures, we resolve the dynamics of photoexcited excitons. We find antiferromagnetic spin arrangement and spin-entangled Zhang-Rice multiplet excitons with lifetimes in the nanosecond range, as well as ultranarrow emission line widths, despite the disordered nature of our films. Thus, our findings demonstrate scalable thin-film fabrication of high-quality NiPS3, which is crucial for translating this 2D antiferromagnetic material into spintronic and nanoscale memory devices and further exploring its complex spin-light coupled states.

Organic Photovoltaic Stability: Understanding the Role of Engineering Exciton and Charge Carrier Dynamics from Recent Progress.

Benefiting from the synergistic development of material design, device engineering, and the mechanistic understanding of device physics, the certified power conversion efficiencies (PCEs) of single-junction non-fullerene organic solar cells (OSCs) have already reached a very high value of exceeding 19%. However, in addition to PCEs, the poor stability is now a challenging obstacle for commercial applications of organic photovoltaics (OPVs). Herein, recent progress made in exploring operational mechanisms, anomalous photoelectric behaviors, and improving long-term stability in non-fullerene OSCs are highlighted from a novel and previously largely undiscussed perspective of engineering exciton and charge carrier pathways. Considering the intrinsic connection among multiple temporal-scale photocarrier dynamics, multi-length scale morphologies, and photovoltaic performance in OPVs, this review delineates and establishes a comprehensive and in-depth property-function relationship for evaluating the actual device stability. Moreover, this review has also provided some valuable photophysical insights into employing the advanced characterization techniques such as transient absorption spectroscopy and time-resolved fluorescence imagings. Finally, some of the remaining major challenges related to this topic are proposed toward the further advances of enhancing long-term operational stability in non-fullerene OSCs.

Veil of the Charge Transfer State in Bay-Annulated Indigo-Based Donor-Acceptor Systems: Charge Separation versus Singlet Fission.

Bay-annulated indigo (BAI) is a new potential SF-active building block, which has aroused great interest in the design of highly stable singlet fission materials. However, singlet fission of unfunctionalized BAI is inactive due to the inappropriate energy levels. Herein, we seek to develop a new design strategy by introducing the charge transfer interaction to tune the exciton dynamics of BAI derivatives. A new donor-acceptor molecule (TPA-2BAI) and two control molecules (TPA-BAI and 2TPA-BAI) were designed and synthesized to unravel the veil of CT states in tuning the excited-state dynamics of BAI derivatives. Transient absorption spectroscopy studies show that CT states are generated immediately following the excitation. However, the low-lying CT states induced by strong donor-acceptor interactions result in them acting as trap states and inhibiting the SF process. These results show that the low-lying CT state is detrimental to SF and provide insight into the design of CT-mediated BAI-based SF materials.

Probing charge carrier and triplet dynamics in TADF-based OLEDs using transient electroluminescence studies

Thermally activated delayed fluorescence (TADF) systems exhibit high emissive yield due to efficient back-conversion of nonemissive triplet states to emissive singlet states via reverse intersystem crossing (RISC). In this paper, both the charge carrier and triplet exciton dynamics are explored using transient electroluminescence (TrEL) measurements in the TADF molecule, 2,3,4,6-Tetra(9H-carbazol-9-yl)-5-fluorobenzonitrile (4CzFCN)-based devices. The analysis of the rising edge of the TrEL pulse indicates that the carriers follow multiple trapping, de-trapping, and exciton recombination dynamics. The trailing edge of the TrEL pulse provides insight into the monomolecular and bimolecular exciton dynamics. These studies along with a kinetic model reveal triplet harvesting processes in a 4CzFCN molecule via both RISC and triplet–triplet annihilation (TTA). Furthermore, at high temperatures, the analysis suggests that TADF processes are dominant with negligible contribution from TTA. The presence of bimolecular triplet processes acts as bottlenecks for accessing higher efficiencies in TADF organic light emitting diodes.

Fermi Pressure and Coulomb Repulsion Driven Rapid Hot Plasma Expansion in a van der Waals Heterostructure.

Transition metal dichalcogenide heterostructures provide a versatile platform to explore electronic and excitonic phases. As the excitation density exceeds the critical Mott density, interlayer excitons are ionized into an electron-hole plasma phase. The transport of the highly non-equilibrium plasma is relevant for high-power optoelectronic devices but has not been carefully investigated previously. Here, we employ spatially resolved pump-probe microscopy to investigate the spatial-temporal dynamics of interlayer excitons and hot-plasma phase in a MoSe2/WSe2 twisted bilayer. At the excitation density of ∼1014 cm-2, well exceeding the Mott density, we find a surprisingly rapid initial expansion of hot plasma to a few microns away from the excitation source within ∼0.2 ps. Microscopic theory reveals that this rapid expansion is mainly driven by Fermi pressure and Coulomb repulsion, while the hot carrier effect has only a minor effect in the plasma phase.

Emergence and Relaxation of an e–h Quantum Liquid Phase in Photoexcited MoS2 Nanoparticles at Room Temperature

AbstractLow‐dimensional transition metal dichalcogenide (TMDC) materials are heralding a new era in optoelectronics and valleytronics owing to their unique properties. Photo‐induced dynamics in these systems is mostly studied from the perspective of individual quasi‐particles—excitons, bi‐excitons, or, even, trions—their formation, evolution, and decay. The role of multi‐body and exciton dynamics, the associated collective behavior, condensation, and inter‐excitonic interactions remain intriguing and seek attention, especially in room‐temperature scenarios that are relevant for device applications. In this work, the formation and decay of an unexpected electron–hole quantum liquid phase at room‐temperature on ultrafast timescales in multi‐layer MoS2 nanoparticles is evidenced through femtosecond broadband transient absorption spectroscopy. The studies presented here reveal the complete dynamical picture: the initial electron–hole plasma (EHP) condenses into a quantum electron–hole liquid (EHL) phase that typically lasts as long as 10 ps, revealing its robustness, whereafter the system decays through phonons. The authors employ a successful physical model using a set of coupled nonlinear rate equations governing the individual populations of these constituent phases to extract their contributions to bandgap renormalization (BGR). Beyond the observation of the electron–hole liquid‐like state at room temperature, this work reveals the ultrafast dynamics of photo‐excited low‐dimensional systems arising out of collective many‐particle behavior and correlations.

Efficient Nanoscale Exciton Transport in Non-Fullerene Organic Solar Cells Enables Reduced Bimolecular Recombination of Free Charges.

The highest-efficiency organic photovoltaic (OPV)-based solar cells, made from blends of electron-donating and electron-accepting organic semiconductors, are often characterized by strongly reduced (non-Langevin) bimolecular recombination. Although the origins of the reduced recombination are debated, mechanisms related to the charge-transfer (CT) state and free-carrier encounter dynamics controlled by the size of donor and acceptor domains are proposed as underlying factors. Here,a novel photoluminescence-based probe is reported to accurately quantify the donor-acceptor domain size in OPV blends. Specifically, the domain size is measured in high-efficiency non-fullerene acceptor (NFA) systems and a comparative conventional fullerene system. It is found that the NFA-based blends form larger domains but that the expected reductions in bimolecular recombination attributed to the enhanced domain sizes are too small to account for the observed reduction factors. Further, it is shown that the reduction of bimolecular recombination is correlated to enhanced exciton dynamics within the NFA domains. This indicates that the processes responsible for efficient exciton transport also enable strongly non-Langevin recombination in high-efficiency NFA-based solar cells with low-energy offsets.

Complex exciton dynamics with elevated temperature in a GaAsSb/GaAs quantum well heterostructure

Exciton dynamics in a GaAsSb/GaAs quantum well (QW) heterostructure were investigated via both steady state and transient photoluminescence. The measurements at 10 K demonstrated the coexistence of localized excitons (LEs) and free excitons (FEs), while a blue-shift resulting from increased excitation intensity indicated their spatially indirect transition (IT) characteristics due to the type-II band alignment. With increasing temperature from 10 K, the LEs and FEs redistribute, with the LEs becoming less intense at relatively higher temperature. With increasing temperature to above 80 K, electrons in GaAs are able to overcome the small band offset to enter inside GaAsSb and recombine with holes; thus, a spatially direct transition (DT) appeared. Hence, we are able to reveal complex carrier recombination dynamics for the GaAsSb/GaAs QW heterostructure, in which the “S” shape behavior is generated not only by the carrier localization but also by the transformation from IT to DT with elevated temperature.

Continuous Making, Stretch Breaking, and Exciton Dynamics of a Red-Emissive Organic Submicrometer-Sized Triangular Pyramid

Highly photoluminescent, single-component self-assembly being scalable and sustainable has a profound commercial significance. In this article, the challenges that we address in development of self-assembly of π-conjugated molecules are ─(i) feeble photoluminescence caused by poor molecular orientational ordering and (ii) costly fluorescent monomer owing to lack of an atom/step/energy economical synthetic method. We have discovered that a bright yellow fluorescent xanthene analog capable of instantly forming self-assembly can be synthesized by a home-built coil-in-spiral reactor using an inexpensive precursor, pyrogallol. Stimuli such as temperature (35 °C), acid fumes, and apolar solvent can trigger the formation of red-emissive self-assembly. In solution orientation of about 13 molecules yielding hydrogen-bonded self-assembly has a direct resemblance with a Coulomb-coupled J-aggregate highlighted in the Kasha model. After photoexcitation, the excited state dynamics of the monomer progress via three pathways: (i) relaxation (2 ± 0.3 ps), (ii) solvation (19.5 ± 3 ps), and (iii) decay (2.5 ns). On the other hand, self-assembly exciton evolves via two pathways: (i) relaxation (81 ± 25 ps) and (ii) decay (∼1 ns). In the solid state, the self-assembly retains the submicron-sized trigonal pyramidal structures by layer-by-layer stacking of triangular plates. This self-assembly doped in polymer even exhibits mechanofluorescence. Our study will pave way the use of this photoluminescent self-assembly for improved performance of organic/sustainable electronics and stretchable electronics.

Impact of cation modification on phonon-dressed exciton dynamics in a prototype two-dimensional hybrid organic-inorganic perovskite system.

Organic-cation engineering has recently proven effective in flexibly regulating two-dimensional hybrid organic-inorganic perovskites (2D HOIPs) to achieve a diversity of newly emerging applications. There have been many mechanistic studies based on the structural tunability of organic cations; nevertheless, those with an emphasis on the effect solely caused by the organic cations remain lacking. To this end, here we deliberately design a set of 2D HOIPs in which the inorganic layers are kept nearly intact upon cation modification, i.e., the precursor phenethylammonium lead iodide and its four derivatives with the phenyl group's para-position H being replaced by CH3, F, Cl, and Br. By means of femtosecond time-resolved transient absorption spectroscopy and temperature-dependent/time-resolved photoluminescence spectroscopy, we interrogate the subtle impact of cation modification on phonon dynamics, coherent phonon modes, phonon-dressed exciton dynamics, and excitonic emissions. A concerted trend for phonon lifetimes and exciton relaxation lifetimes regulated by cation modification is revealed, evidencing the existence of strong exciton-phonon coupling in this 2D HOIP system. The observed mass effect can be ascribed to the change in moment of inertia of organic cations. In addition, we observe an interesting interplay of exciton kinetics pertinent to population transfers between two emissive states, likely linked to the subtle variation in crystal symmetry induced by cation modification. The mechanistic insights gained from this work would be of value for the 2D HOIPs-based applications.

Effect of Fluorinated End-Groups on the Exciton Dynamics and Charge Transfer of Non-fused Ring Acceptors

In recent years, the optimization of non-fused ring electron acceptors (NFREAs) has become an important topic, which includes π extension, side-chain engineering, and end-group halogenation. While the performance characterization of different NFREAs, including their morphology and power conversion efficiencies, has been extensively studied, the influence of different optimization methods on their photophysical processes is not clear. Here, we analyze the effect of end-group fluoridation on exciton dynamics and charge transfer (CT) in NFREA-based organic photovoltaics in detail using a novel NFREA Isopropyl-0F and its end-group fluorinated homologue Isopropyl-2F by means of spectroscopy, in order to understand the physical mechanism for the differences in their performance. The transient absorption spectra show that the more ordered molecular arrangement in the Isopropyl-2F-based heterojunction resulted in faster exciton diffusion and higher hole transfer efficiency, which were conducive to CT and reduced recombination loss. These results well explain the improved properties after end-group fluoridation.

Exciton Lifetime and Optical Line Width Profile via Exciton-Phonon Interactions: Theory and First-Principles Calculations for Monolayer MoS2.

Exciton dynamics dictates the evolution of photoexcited carriers in photovoltaic and optoelectronic devices. However, interpreting their experimental signatures is a challenging theoretical problem due to the presence of both electron-phonon and many-electron interactions. We develop and apply here a first-principles approach to exciton dynamics resulting from exciton-phonon coupling in monolayer MoS2 and reveal the highly selective nature of exciton-phonon coupling due to the internal spin structure of excitons, which leads to a surprisingly long lifetime of the lowest-energy bright A exciton. Moreover, we show that optical absorption processes rigorously require a second-order perturbation theory approach, with photon and phonon treated on an equal footing, as proposed by Toyozawa and Hopfield. Such a treatment, thus far neglected in first-principles studies, gives rise to off-diagonal exciton-phonon self-energy, which is critical for the description of dephasing mechanisms and yields exciton line widths in excellent agreement with experiment.

Layer-dependent correlated phases in WSe2/MoS2 moiré superlattice.

Electron correlation plays an essential role in the macroscopic quantum phenomena in the moiré heterostructure, such as antiferromagnetism and correlated insulating phases. Unlike the phenomena where the interaction involves only electrons in one layer, the interaction of distinct phases in two or more layers represents a new horizon forward, such as the one in the Kondo lattice model. Here, using interlayer excitons as a probe, we show that the interlayer interactions in heterobilayers of tungsten diselenide and molybdenum disulfide (WSe2/MoS2) can be electrically switched on and off, resulting in a layer-dependent correlated phase diagram, including single-layer, layer-selective, excitonic-insulator and layer-hybridized regions. We demonstrate that these correlated phases affect the interlayer exciton non-radiative decay pathways. These results reveal the role of strong correlation on interlayer exciton dynamics and pave the way for studying the layer-resolved strong correlation behaviour in moiré heterostructures.