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The electronic and optical properties of 2D transition metal dichalcogenides are dominated by strong excitonic resonances. Exciton dynamics plays a critical role in the functionality and performance of many miniaturized 2D optoelectronic devices; however, the measurement of nanoscale excitonic behaviors remains challenging. Here, a near-field transient nanoscopy is reported to probe exciton dynamics beyond the diffraction limit. Exciton recombination and exciton-exciton annihilation processes in monolayer and bilayer MoS2 are studied as the proof-of-concept demonstration. Moreover, with the capability to access local sites, intriguing exciton dynamics near the monolayer-bilayer interface and at the MoS2 nano-wrinkles are resolved. Such nanoscale resolution highlights the potential of this transient nanoscopy for fundamental investigation of exciton physics and further optimization of functional devices.

Doping 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. [ABSTRACT FROM AUTHOR]

Lead‐free hybrid metal halide phosphors/crystals showing self‐trapped exciton (STE) emission have been recently explored for thermography due to the strong temperature dependence of their photoluminescence (PL) lifetime (τ). However, realizing high‐spatial‐resolution thermography using polycrystalline powders or crystals presents a challenge. Moreover, the underlying mechanism of temperature‐dependent STE remains elusive. Herein, a homogeneous 1D ODASn2I6 (ODA, 1,8‐octanediamine) nm‐scale thin film exhibiting efficient STE emission is investigated. The PL decay shows a strong temperature dependence from 275 K (τ ≈ 1.31 µs) to 350 K (τ ≈ 0.65 µs) yielding a thermal sensitivity of 0.014 K−1. By employing temperature‐dependent transient absorption spectroscopy, detailed information is obtained about the relaxation processes prior to the STE formation. Simultaneous analyses of steady‐state and time‐resolved spectroscopies lead to a self‐consistent model where the thermally activated phonon‐assisted nonradiative pathway explains the temperature dependence of the PL lifetime via a conical intersection between the ground state and STE potential energy surfaces. Finally, a discernible 50 ns variation in PL lifetimes across different heated regimes over a distance of 1.15 mm is successfully demonstrated with fluorescence lifetime imaging microscopy, underscoring the substantial potential of ODASn2I6 thin film for high‐spatial‐resolution thermography. [ABSTRACT FROM AUTHOR]

Up‐conversion of triplet into singlet exciton in the emitting layer is believed to be one of the ways that thermally activated delayed fluorescent (TADF) materials may employ to reduce triplet exciton density hence preventing device quenching by triplet excitons. Yet, two donor‐acceptor type molecules; 5‐(4‐(4,6‐diphenyl‐1,3,5‐triazin‐2‐yl)phenyl)‐12‐(3‐(triphenylsilyl) phenyl)‐5,12‐dihydroindolo[3,2‐a]carbazole (SiPhCzTrz) and 5‐phenyl‐12‐(4‐(4‐phenyl‐6‐(3‐(triphenylsilyl) phenyl)‐1,3,5‐triazin‐2‐yl)pheny‐l)‐5,12‐dihydroindolo [3,2‐a]carbazole (SiTrzPhCz), which exhibited different TADF properties depending on the relative positions of their electron donor unit (PhCz) and electron acceptor unit (Trz), show opposite behaviors. These materials are used as sensitizer in phosphorescent solution‐processed organic light emitting diodes (s‐OLEDs) showing moderately high current efficiencies of 19.3 and 20 cd/A, respectively. SiTrzPhCz exhibits stronger TADF properties compared to SiPhCzTrz; however, these stronger TADF characteristics lead to a more pronounced efficiency roll‐off, mainly due to the longer residence time of excitons in SiTrzPhCz, leading to exciton quenching. In contrast, due to their twisted structures, the efficiency roll‐off is efficiently suppressed, particularly for SiTrzPhCz, when both materials are used as hosts. Their twisted structures promote aggregate‐induced emission and prevent aggregation‐caused quenching. Further analysis of exciton dynamics reveals faster decay rate for both singlet and triplet densities in SiPhCzTrz compared to SiTrzPhCz, indicated by its higher fast prompt emission, kFRET and knrT. [ABSTRACT FROM AUTHOR]

A fully quantum, numerically accurate methodology is presented for the simulation of the exciton dynamics and time-resolved fluorescence of cavity-tuned two-dimensional (2D) materials at finite temperatures. This approach was specifically applied to a monolayer WSe2 system. Our methodology enabled us to identify the dynamical and spectroscopic signatures of polaronic and polaritonic effects and to elucidate their characteristic timescales across a range of exciton–cavity couplings. The approach employed can be extended to simulation of various cavity-tuned 2D materials, specifically for exploring finite temperature nonlinear spectroscopic signals. [ABSTRACT FROM AUTHOR]

A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL‐R) or ethylene glycol‐based bridge chains (CL‐TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL‐TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5‐fold compared to that obtained using non‐crosslinked F8BT photocatalysts, whereas CL‐R‐based photocatalysts yield HER rates comparable to those of non‐crosslinked counterparts. Photophysical analyses including time‐resolved photoluminescence and transient absorption measurements reveal that adding CL‐TEG accelerates exciton separation, forming long‐lived charge carriers. Additionally, the in‐depth study using molecular dynamics simulations elucidates the dual role of CL‐TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high‐permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts. [ABSTRACT FROM AUTHOR]

Porphyrin‐based metal‐organic frameworks (MOFs) have received great attention for solar photochemistry applications. Manipulating the direction of energy (exciton) migration plays an essential role in boosting the light‐harvesting efficiency of porphyrin‐based MOFs. Here, based on the time‐dependent exciton‐exciton annihilation rate, an optical control of directional exciton migration is demonstrated in cobalt‐porphyrin surface‐supported MOF nanofilms (Co‐TCPP SURMOFs). Utilizing photocarrier densities or lattice temperature as the control knob, the dynamic form of exciton migration in Co‐TCPP SURMOFs can be switched between the nearest‐neighbor 1D interaction and the quasi‐isotropic 2D interaction, which is well explained using a diffusion model of exciton‐exciton scattering. This results provide an optical approach to regulating exciton migration in MOFs, which enhances understanding of the excitonic behavior in artificial light harvesters. [ABSTRACT FROM AUTHOR]

Primary excitation energy transfer and charge separation in photosystem I (PSI) from the extremophile desert green alga Chlorella ohadii grown in low light were studied using broadband femtosecond pump-probe spectroscopy in the spectral range from 400 to 850 nm and in the time range from 50 fs to 500 ps. Photochemical reactions were induced by the excitation into the blue and red edges of the chlorophyll Qy absorption band and compared with similar processes in PSI from the cyanobacterium Synechocystis sp. PCC 6803. When PSI from C. ohadii was excited at 660 nm, the processes of energy redistribution in the light-harvesting antenna complex were observed within a time interval of up to 25 ps, while formation of the stable radical ion pair P700+A1− was kinetically heterogeneous with characteristic times of 25 and 120 ps. When PSI was excited into the red edge of the Qy band at 715 nm, primary charge separation reactions occurred within the time range of 7 ps in half of the complexes. In the remaining complexes, formation of the radical ion pair P700+A1− was limited by the energy transfer and occurred with a characteristic time of 70 ps. Similar photochemical reactions in PSI from Synechocystis 6803 were significantly faster: upon excitation at 680 nm, formation of the primary radical ion pairs occurred with a time of 3 ps in ~30% complexes. Excitation at 720 nm resulted in kinetically unresolvable ultrafast primary charge separation in 50% complexes, and subsequent formation of P700+A1− was observed within 25 ps. The photodynamics of PSI from C. ohadii was noticeably similar to the excitation energy transfer and charge separation in PSI from the microalga Chlamydomonas reinhardtii; however, the dynamics of energy transfer in C. ohadii PSI also included slower components. [ABSTRACT FROM AUTHOR]

In this paper, we implemented new time dependent exciton decay model based on exciton dynamics using transient electroluminescence profile of fluorescent triplet‐triplet annihilation (TTA) orgarnic light‐emitting diodes (OLEDs). The prompt and delayed components of fluorescent TTA OLED could be distinguished quantitatively and accurate TTA ratio analysis was achieved using the new TTA model. In addition, predictive model of kinetic coefficients and TTA ratio was established using neural network of multilayer perception, and it demonstrated nearly perfect prediction ability of TTA ratio (determination coefficient, R2 = 0.999). The results of this study would contribute to understand TTA mechanisms deeply with exact estimation of major parameters of TTA OLEDs and help future OLED research using deep learning predictive model. [ABSTRACT FROM AUTHOR]

Layered halide perovskites exhibit remarkable optoelectronic properties and technological promise, driven by strongly bound excitons. The interplay of spin‐orbit and exchange coupling creates a rich excitonic landscape, determining their optical signatures and exciton dynamics. Despite the dark excitonic ground state, surprisingly efficient emission from higher‐energy bright states has puzzled the scientific community, sparking debates on relaxation mechanisms. Combining low‐temperature magneto‐optical measurements with sophisticated many‐particle theory, the origin of the bright exciton emission in perovskites is elucidated by tracking the thermalization of dark and bright excitons under a magnetic field. The unexpectedly high emission is clearly attributed to a pronounced phonon‐bottleneck effect, considerably slowing down the relaxation toward the energetically lowest dark states. It is demonstrated that this bottleneck can be tuned by manipulating the bright‐dark energy splitting and optical phonon energies, offering valuable insights and strategies for controlling exciton emission in layered perovskite materials that is crucial for optoelectronics applications. [ABSTRACT FROM AUTHOR]

Exciton dynamics in π-conjugated polymers systems encompass multiple time and length scales. Ultrafast femtosecond processes are intrachain and involve a quantum mechanical correlation of the exciton and nuclear degrees of freedom. In contrast, post-pico-second processes involve the incoherent Förster transfer of excitons between polymer chains. Exciton dynamics is also strongly determined by the spatial and temporal disorder that is ubiquitous in conjugated polymers. Since excitons are delocalized over hundreds of atoms, a theoretical understanding of these processes is only realistically possible by employing suitably parametrized coarse-grained exciton-phonon models. Moreover, to correctly account for ultrafast processes, the exciton and phonon modes must be treated on the same quantum mechanical basis and the Ehrenfest approximation must be abandoned. This further implies that sophisticated numerical techniques must be employed to solve these models. This review describes our current theoretical understanding of exciton dynamics in conjugated polymer systems. We begin by describing the energetic and spatial distribution of excitons in disordered polymer systems, and define the crucial concept of a "chromophore" in conjugated polymers. We also discuss the role of exciton-nuclear coupling, emphasizing the distinction between "fast" and "slow" nuclear degrees of freedom in determining "self-trapping" and "self-localization" of exciton-polarons. Next, we discuss ultrafast intrachain exciton decoherence caused by exciton-phonon entanglement, which leads to fluorescence depolarization on the timescale of 10-fs. Interactions of the polymer with its environment causes the stochastic relaxation and localization of high-energy delocalized excitons onto chromophores. The coupling of excitons with torsional modes also leads to various dynamical processes. On sub-ps timescales it causes exciton-polaron formation (i.e., exciton localization and local polymer planarization). Conversely, on post-ps timescales stochastic torsional fluctuations cause exciton-polaron diffusion along the polymer chain and at higher temperatures to transient exciton delocalization via extended exciton states. We next describe a firstprinciples, Förster-type model of interchain exciton transfer and diffusion in the condensed phase, whose starting point is a realistic description of the donor and acceptor chromophores. Finally, we discuss condensed phase transient exciton delocalization in highly-ordered nanofibers. We survey experimental results and explain how they can be understood in terms of our theoretical description of exciton dynamics coupled to information on polymer multiscale structures. The review also contains a brief critique of computational methods to simulate exciton dynamics. [ABSTRACT FROM AUTHOR]

Abstract A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL‐R) or ethylene glycol‐based bridge chains (CL‐TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL‐TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5‐fold compared to that obtained using non‐crosslinked F8BT photocatalysts, whereas CL‐R‐based photocatalysts yield HER rates comparable to those of non‐crosslinked counterparts. Photophysical analyses including time‐resolved photoluminescence and transient absorption measurements reveal that adding CL‐TEG accelerates exciton separation, forming long‐lived charge carriers. Additionally, the in‐depth study using molecular dynamics simulations elucidates the dual role of CL‐TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high‐permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.

Two-dimensional (2D) layered materials exhibit strong light-matter interactions, remarkable excitonic effects, and ultrafast optical response, making them promising for high-speed on-chip nanophotonics. Recently, significant attention has been directed towards anisotropic 2D materials (A2DMs) with low in-plane crystal symmetry. These materials present unique optical properties dependent on polarization and direction, offering additional degrees of freedom absent in conventional isotropic 2D materials. In this review, we discuss recent progress in understanding the fundamental aspects and ultrafast nanophotonic applications of A2DMs. We cover structural characteristics and anisotropic linear/nonlinear optical properties of A2DMs, including well-studied black phosphorus and rhenium dichalcogenides, as well as emerging quasi-one-dimensional materials. Then, we discuss fundamental ultrafast anisotropic phenomena occurring in A2DMs, such as polarization-dependent ultrafast dynamics of charge carriers and excitons, their direction-dependent spatiotemporal diffusion, photo-induced symmetry switching, and anisotropic coherent acoustic phonons. Furthermore, we review state-of-the-art ultrafast nanophotonic applications based on A2DMs, including polarization-driven active all-optical modulations and ultrafast pulse generations. This review concludes by offering perspectives on the challenges and future prospects of A2DMs in ultrafast nanophotonics.

With the rapid increase in power conversion efficiency of organic photovoltaics due to the development of non‐fullerene acceptors (NFAs), prolonging the operational lifetime of devices becomes one of the critical prerequisites for commercial application. In this work, the degradation pathways of a wide range of state‐of‐the‐art NFA molecules via multiple spectroscopic techniques combined with density functional theory and molecular dynamics simulation are revealed. The structural confinement and molecular ordering are responsible for molecular conformational stability under illumination. More importantly, a very general trend is revealed that the origin of increased nonradiative decay under illumination is predominately in the aggregated states with strong intermolecular interactions while the intramolecular exciton dynamics are stable. The increased nonradiative decay correlates with reduced exciton diffusion length. This work provides vital information toward the design of intrinsically photo‐stable NFAs at the molecular level and the importance of aggregation control toward long‐term stable organic solar cells. [ABSTRACT FROM AUTHOR]

In a previous study, we proposed an open quantum network model of a quantum battery (QB) that possesses dark states owing to its structural exchange symmetries. While in a dark state, the QB is capable of storing an exciton without any environment-induced population losses. However, when the structural exchange symmetry is broken, the QB begins to discharge the exciton towards its exit site. In this article, we start by demonstrating that this QB is not only loss-free with respect to exciton population during the storage phase, but also with respect to the QB energy. We then explore the exciton population and energy transfer dynamics of the QB during the discharge phase over a wide range of site energies, bath temperatures, and bath reorganization energies. Our results shed light on how to optimize the QB's population and energy transfer dynamics for different purposes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The optical properties of doped metal nanoclusters (NCs) have stimulated great research interests because of their applications in biosensing and photocatalysis. The photoluminescence and excited state dynamics of MAu24(SR)18 are complicated and the detailed mechanism has not been fully understood. Here, we investigate the exciton and vibrational dynamics of two doped NCs MAu24(SR)18 (M=Pd, Pt; SR stands for phenylethanethiolate) by ultrafast spectroscopy. In contrast to the parent Au25(SR)18 NCs, Pd and Pt doping significantly reduce the exciton lifetime by several orders of magnitude. We find that the ultrashort exciton lifetimes of PtAu24 (5 ps) and PdAu24 (30 ps) are ascribed to the ultrasmall energy gap (Eg=0.3 eV). In both two doped NCs, we observe significant coherent vibrations (2.4 THz) that arise from the metal core, which indicates these oscillations can survive regardless of the short exciton lifetime. Unravelling the effect of foreign atom doping on the exciton and vibrational dynamics of metal NCs will provide new insight into their optical properties and help designing these molecular-like nanostructures for specific applications. [ABSTRACT FROM AUTHOR]

Mixed dimensional van der Waals heterostructure based on layered two-dimensional molybdenum disulfide (MoS2) interfaced to gallium nitride (GaN) has attracted tremendous attention due to its unique properties and application in novel electronic, optoelectronic, and quantum devices. However, developing facile synthesis methods and insights into the exciton dynamics for this system still remains a major challenge. Here, a simple and cost-effective method is demonstrated for large-scale synthesis of monolayer MoS2 on differently doped GaN substrates. A mixed aqueous solution of Na2MoO4 and NaOH is spin-coated on GaN and sulfurated in one step by chemical vapor deposition (CVD). High quality monolayer MoS2 nanosheets with side length over 400 μm and surface coverage ratio of more than 90 % are achieved on GaN. Furthermore, the PL intensity, excitonic transition ratios and ultrafast exciton dynamics of MoS2 are observed to be largely modulated by the doping type of GaN, owing to substrate-induced doping, which is proved by Raman, PL and transient absorption spectroscopy. Notably, p-GaN can attract electrons from monolayer MoS2 and weaken its intrinsic n-doping, thereby facilitating higher PL intensity as well as longer exciton lifetime, while n-GaN provides strong n-doping and generates opposite effect. This work hereby presents a pathway for large-scale synthesis of MoS2/GaN heterostructures and further understanding of their charge transfer properties and exciton dynamics, which should inspire their applications for optoelectronic devices. [ABSTRACT FROM AUTHOR]

Mixed dimensional van der Waals heterostructure based on layered two-dimensional molybdenum disulfide (MoS2) interfaced to gallium nitride (GaN) has attracted tremendous attention due to its unique properties and application in novel electronic, optoelectronic, and quantum devices. However, developing facile synthesis methods and insights into the exciton dynamics for this system still remains a major challenge. Here, a simple and cost-effective method is demonstrated for large-scale synthesis of monolayer MoS2 on differently doped GaN substrates. A mixed aqueous solution of Na2MoO4 and NaOH is spin-coated on GaN and sulfurated in one step by chemical vapor deposition (CVD). High quality monolayer MoS2 nanosheets with side length over 400 μm and surface coverage ratio of more than 90 % are achieved on GaN. Furthermore, the PL intensity, excitonic transition ratios and ultrafast exciton dynamics of MoS2 are observed to be largely modulated by the doping type of GaN, owing to substrate-induced doping, which is proved by Raman, PL and transient absorption spectroscopy. Notably, p-GaN can attract electrons from monolayer MoS2 and weaken its intrinsic n-doping, thereby facilitating higher PL intensity as well as longer exciton lifetime, while n-GaN provides strong n-doping and generates opposite effect. This work hereby presents a pathway for large-scale synthesis of MoS2/GaN heterostructures and further understanding of their charge transfer properties and exciton dynamics, which should inspire their applications for optoelectronic devices.

A fully quantum, numerically accurate methodology is presented for the simulation of the exciton dynamics and time-resolved fluorescence of cavity-tuned two-dimensional (2D) materials at finite temperatures. This approach was specifically applied to a monolayer WSe2 system. Our methodology enabled us to identify the dynamical and spectroscopic signatures of polaronic and polaritonic effects and to elucidate their characteristic timescales across a range of exciton–cavity couplings. The approach employed can be extended to simulation of various cavity-tuned 2D materials, specifically for exploring finite temperature nonlinear spectroscopic signals.

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. [ABSTRACT FROM AUTHOR]

Low photoluminescence (PL) quantum yield of molybdenum disulfide (MoS2) quantum dots (QDs) has limited practical application as potential fluorescent materials. Here, we report the intercalation of aluminum ion (Al3+) to enhance the PL of MoS2 QDs and the underlying mechanism. With detailed characterization and exciton dynamics study, we suggest that additional surface states including new emission centers have been effectively introduced to MoS2 QDs by the Al3+ intercalation. The synergy of new radiative pathway for exciton recombination and the passivation of non-radiative surface traps is responsible for the enhanced fluorescence of MoS2 QDs. Our findings demonstrate an efficient strategy to improve the optical properties of MoS2 QDs and are important for understanding the regulation effect of surface states on the emission of two dimensional sulfide QDs. [ABSTRACT FROM AUTHOR]

Low‐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. [ABSTRACT FROM AUTHOR]

Polymer composites based on polycarbonate (PC) and polyether ether ketone (PEEK) filled with single-walled carbon nanotubes (SWCNTs, 0.5–2.0 wt %) were melt-mixed to investigate their suitability for thermoelectric applications. Both types of polymer composites exhibited positive Seebeck coefficients (S), indicative for p-type thermoelectric materials. As an additive to improve the thermoelectric performance, three different ionic liquids (ILs), specifically THTDPCl, BMIMPF6, and OMIMCl, were added with the aim to change the thermoelectric conduction type of the composites from p-type to n-type. It was found that in both composite types, among the three ILs employed, only the phosphonium-based IL THTDPCl was able to activate the p- to n-type switching. Moreover, it is revealed that for the thermoelectric parameters and performance, the SWCNT:lL ratio plays a role. In the selected systems, S-values between 61.3 μV/K (PEEK/0.75 wt % SWCNT) and −37.1 μV/K (PEEK/0.75 wt % SWCNT + 3 wt % THTDPCl) were reached. In order to shed light on the physical origins of the thermoelectric properties, the PC-based composites were studied using ultrafast laser time-resolved transient absorption spectroscopy (TAS). The TAS studies revealed that the introduction of ILs in the developed PC/CNT composites leads to the formation of biexcitons when compared to the IL-free composites. Moreover, no direct correlation between S and exciton lifetimes was found for the IL-containing composites. Instead, the exciton lifetime decreases while the conductivity seems to increase due to the availability of more free-charge carriers in the polymer matrix. [ABSTRACT FROM AUTHOR]

The extreme confinement and reduced screening in monolayer transition metal dichalcogenides (TMDs) leads to the appearance of tightly bound excitons which can also couple to free charges, forming trions, owing to strong Coulomb interactions. Low temperatures and encapsulation in hexagonal boron nitride (hBN) can narrow the excitonic linewidth, approaching the regime of homogeneous broadening, mostly dominated by the radiative decay. Ultrafast spectroscopy is a perfect tool to study exciton formation and relaxation dynamics in TMD monolayers. However, high‐quality hBN‐encapsulated structures have usually lateral sizes of the order of a few micrometers, calling for the combination of high spatial and temporal resolution in pump–probe experiments. Herein, a custom broadband pump–probe optical microscope is used to measure the ultrafast dynamics of neutral and charged excitons in high‐quality hBN‐encapsulated monolayer MoS2 at 8 K. Neutral excitons exhibit a narrow linewidth of 7.5 meV, approaching the homogeneous limit, which is related to the fast recombination time of ≈130 fs measured in pump–probe. Moreover, markedly different dynamics of the trions over the neutral ones are observed. The results provide novel insights on the exciton recombination processes in TMD monolayers, paving the way for exploring the ultrafast behavior of excitons and their many‐body complexes in TMD heterostructures. [ABSTRACT FROM AUTHOR]

The operational lifetime of blue organic light‐emitting diodes (OLEDs) is still insufficient for practical applications in lighting and display. One type of blue organic emitting materials with hybridized local and charge‐transfer (HLCT) process are beneficial in achieving high‐efficiency OLEDs through "hot exciton" channel by harnessing high‐lying triplet (Tn) excitons. However, the operational lifetime of the resulting blue OLEDs is rarely studied and understood. In this article, the aging properties of blue fluorescent OLEDs based on an HLCT material (2‐(4‐(10‐(3‐(9H‐carbazol‐9‐yl)phenyl)anthracen‐9‐yl)phenyl)‐1‐phenyl‐1H‐phenanthro[9,10‐d]imidazole) (PAC) are systematically investigated by exciton dynamics calculation and transient EL experiments. It is experimentally and theoretically revealed that whether the reverse intersystem crossing (hRISC) process from high‐lying excited triplet to singlet in HLCT materials is completely effective determines the device degradation. A fluorescent emitter is doped into PAC host to accelerate the hRISC process, thus enhancing device operational lifetime to reach T75 = 110 ± 2 h (time to 75% of initial luminance) under 1000 cd m−2. This work provides inspirations to investigate the stability of blue fluorescent OLEDs based on HCLT materials and further enhance the operational lifetime. [ABSTRACT FROM AUTHOR]

In this mini review, we focus on recent advances in the atomistic modeling of biological light-harvesting (LH) complexes. Because of their size and sophisticated electronic structures, multiscale methods are required to investigate the dynamical and spectroscopic properties of such complexes. The excitation energies, in this context also known as site energies, excitonic couplings, and spectral densities are key quantities which usually need to be extracted to be able to determine the exciton dynamics and spectroscopic properties. The recently developed multiscale approach based on the numerically efficient density functional tight-binding framework followed by excited state calculations has been shown to be superior to the scheme based on pure classical molecular dynamics simulations. The enhanced approach, which improves the description of the internal vibrational dynamics of the pigment molecules, yields spectral densities in good agreement with the experimental counterparts for various bacterial and plant LH systems. Here, we provide a brief overview of those results and described the theoretical foundation of the multiscale protocol. [ABSTRACT FROM AUTHOR]

In a previous study, we proposed an open quantum network model of a quantum battery (QB) that possesses dark states owing to its structural exchange symmetries. While in a dark state, the QB is capable of storing an exciton without any environment-induced population losses. However, when the structural exchange symmetry is broken, the QB begins to discharge the exciton towards its exit site. In this article, we start by demonstrating that this QB is not only loss-free with respect to exciton population during the storage phase, but also with respect to the QB energy. We then explore the exciton population and energy transfer dynamics of the QB during the discharge phase over a wide range of site energies, bath temperatures, and bath reorganization energies. Our results shed light on how to optimize the QB’s population and energy transfer dynamics for different purposes.

The unraveling of open quantum system dynamics in terms of stochastic quantum trajectories offers a picture of open system dynamics that consistently considers memory effects stemming from the finite correlation time of environment fluctuations. These fluctuations significantly influence the coherence and energy transport properties of excitonic systems. When their correlation time is comparable to the timescale of the Hamiltonian evolution, it leads to the departure of open system dynamics from the Markovian limit. In this work, we leverage the unraveling of exciton dynamics through stochastic Hamiltonian propagators to design quantum circuits that simulate exciton transport, capturing finite memory effects. In addition to enabling the synthesis of parametrizable quantum circuits, stochastic unitary propagators provide a transparent framework for investigating non-Markovian effects on exciton transport. Our analysis reveals a nuanced relationship between environment correlation time and transport efficiency, identifying a regime of ‘memory-assisted’ quantum transport where time-correlated fluctuations allow the system to reach higher efficiency. However, this property is not universal and can only be realized in conjunction with specific features of the system Hamiltonian.

The surface chemistry and inter-connectivity within perovskite nanocrystals play a critical role in determining the electronic interactions. They manifest in the Coulomb screening of electron–hole correlations and the carrier relaxation dynamics, among other many-body processes. Here, we characterize the coupling between the exciton and free carrier states close to the band-edge in a ligand-free formamidinium lead bromide nanocrystal assembly via two-dimensional coherent spectroscopy. The optical signatures observed in this work show: (i) a nonlinear spectral lineshape reminiscent of Fano-like interference that evidences the coupling between discrete electronic states and a continuum, (ii) symmetric excited state absorption cross-peaks that suggest the existence of a coupled exciton-carrier excited state, and (iii) ultrafast carrier thermalization and exciton formation. Our results highlight the presence of coherent coupling between exciton and free carriers, particularly in the sub-100 femtosecond timescales.

Exciton dynamics in ReS2 are rich and complicated due to its unique lattice and band structures. With femtosecond pump‐probe spectroscopy, the wavelength‐dependent exciton dynamics in bulk ReS2 are studied at room temperature, and the effects from polarization and stacking order are also considered. Signatures from both bright and dark excitons are observed, where the lifetime at bright exciton levels is only several picoseconds, while it is about tens of picoseconds at dark exciton levels. The extremely long up‐/down‐going trend at selective wavelengths is attributed to the transition between different dark exciton levels. Two types of coherent dynamics are observed when the laser wavelength is scanned through different exciton levels: coherent optical stark effect and exciton‐exciton coherent interaction, both occurring within the laser pulse width. Exciton dynamics show a similar trend for the sample with AA stacking order, regardless of polarization. For AB stacking, dark excitons for Exciton II and III are missing when probe pulse polarization is perpendicular to b‐axis, which is attributed to the polarization and stacking‐order dependent band structure. Studying the rich exciton dynamics in bulk ReS2 at room temperature not only has scientific significance, but also facilitates the development of high‐performance excitonic devices. [ABSTRACT FROM AUTHOR]

Exciton dynamics in ReS2 are rich and complicated due to its unique lattice and band structures. With femtosecond pump‐probe spectroscopy, the wavelength‐dependent exciton dynamics in bulk ReS2 are studied at room temperature, and the effects from polarization and stacking order are also considered. Signatures from both bright and dark excitons are observed, where the lifetime at bright exciton levels is only several picoseconds, while it is about tens of picoseconds at dark exciton levels. The extremely long up‐/down‐going trend at selective wavelengths is attributed to the transition between different dark exciton levels. Two types of coherent dynamics are observed when the laser wavelength is scanned through different exciton levels: coherent optical stark effect and exciton‐exciton coherent interaction, both occurring within the laser pulse width. Exciton dynamics show a similar trend for the sample with AA stacking order, regardless of polarization. For AB stacking, dark excitons for Exciton II and III are missing when probe pulse polarization is perpendicular to b‐axis, which is attributed to the polarization and stacking‐order dependent band structure. Studying the rich exciton dynamics in bulk ReS2 at room temperature not only has scientific significance, but also facilitates the development of high‐performance excitonic devices. [ABSTRACT FROM AUTHOR]

The rate constants that describe the decays of excited states (free charge carriers, excitons) are important parameters for perovskite materials. Typically, these rates are determined using detectors with high time‐resolution to record the time‐dependent photoluminescence on the nanosecond scale. Herein, a method is applied that uses two excitation pulses with a variable delay and an inexpensive detector capable of measuring only the quasisteady state photoluminescence. Based on how the time‐integrated photoluminescence varies as a function of the delay time between the two excitation pulses, the rate constants for exciton–exciton annihilation, monomolecular exciton decay, bimolecular free charge carrier recombination, and monomolecular trapping of free charge carriers can be extracted. To demonstrate the method quasi‐2D perovskites are investigated as they are known to exhibit excited‐state populations that can be exciton dominated, free charge carrier dominated, or a mixture of the two. The method leads to unique curves and accurate extracted parameters in all cases. The introduced method of determining excited‐state lifetimes can be used with detectors that only have a low temporal resolution. This opens the path to the spatial mapping of excited‐state dynamics using standard cameras which would be attractive for quality control of photovoltaic layers. [ABSTRACT FROM AUTHOR]

Ag x Se ( x > 2) colloidal quantum dots (CQDs) have recently emerged as a promising environmentally friendly material contender for mid- and long-wave infrared optoelectronics, leveraging their intraband transition (1S e -1P e ). However, multicarrier interactions in CQDs, particularly Auger recombination, have profound implications on the optoelectronic properties of the materials and their potential in device applications. Understanding the intraband excited-state dynamics in n-doped Ag x Se is therefore essential for the assessment and successful implementation of this material platform in devices. We, herein, investigate the carrier dynamics of Ag x Se in both solution and thin-film states using a femtosecond mid-infrared transient absorption spectrometer. Our observations reveal that the multicarrier Auger process depends on the degree of doping in Ag x Se CQDs and accelerates when the Fermi energy ( E F ) level approaches the 1P e state. The calculated intraband Auger coefficients ( C A ) are measured to be on the order of ∼10 -28 cm 6 s -1 , significantly larger compared to analogous n-doped HgS/Se CQDs.

This study examines the exciton dynamics in InGaN/GaN core-shell nanorods using time-resolved cathodoluminescence (TRCL), which provides nanometer-scale lateral spatial and tens of picoseconds temporal resolutions. The focus is on thick (>20 nm) InGaN layers on the non-polar, semi-polar and polar InGaN facets, which are accessible for study due to the unique nanorod geometry. Spectrally integrated TRCL decay transients reveal distinct recombination behaviours across these facets, indicating varied exciton lifetimes. By extracting fast and slow lifetime components and observing their temperature trends along with those of the integrated and peak intensity, the differences in behaviour were linked to variations in point defect density and the degree and density of localisation centres in the different regions. Further analysis shows that the non-polar and polar regions demonstrate increasing lifetimes with decreasing emission energy, attributed to an increase in the depth of localisation. This investigation provides insights into the intricate exciton dynamics in InGaN/GaN nanorods, offering valuable information for the design and development of optoelectronic devices., (Creative Commons Attribution license.)

Abstract Van der Waals heterostructures built by vertically stacked transition metal dichalcogenides (TMDs) exhibit a rich energy landscape, including interlayer and intervalley excitons. Recent experiments demonstrated an ultrafast charge transfer in TMD heterostructures. However, the nature of the charge transfer process has remained elusive. Based on a microscopic and material‐realistic exciton theory, we reveal that phonon‐mediated scattering via strongly hybridized intervalley excitons governs the charge transfer process that occurs on a sub‐100fs timescale. We track the time‐, momentum‐, and energy‐resolved relaxation dynamics of optically excited excitons and determine the temperature‐ and stacking‐dependent charge transfer time for different TMD bilayers. The provided insights present a major step in microscopic understanding of the technologically important charge transfer process in van der Waals heterostructures. Key Points Microscopic and fully quantum‐mechanic model is developed to calculate exciton dynamics in van der Waals heterostructures Charge transfer occurs on a femtosecond timescale and is a phonon‐mediated two‐step process Strongly hybridized dark exciton states play a crucial role for the charge transfer

Exciton dynamics in π-conjugated polymers systems encompass multiple time and length scales. Ultrafast femtosecond processes are intrachain and involve a quantum mechanical correlation of the exciton and nuclear degrees of freedom. In contrast, post-picosecond processes involve the incoherent Förster transfer of excitons between polymer chains. Exciton dynamics is also strongly determined by the spatial and temporal disorder that is ubiquitous in conjugated polymers. Since excitons are delocalized over hundreds of atoms, a theoretical understanding of these processes is only realistically possible by employing suitably parametrized coarse-grained exciton-phonon models. Moreover, to correctly account for ultrafast processes, the exciton and phonon modes must be treated on the same quantum mechanical basis and the Ehrenfest approximation must be abandoned. This further implies that sophisticated numerical techniques must be employed to solve these models. This review describes our current theoretical understanding of exciton dynamics in conjugated polymer systems. We begin by describing the energetic and spatial distribution of excitons in disordered polymer systems, and define the crucial concept of a “chromophore” in conjugated polymers. We also discuss the role of exciton-nuclear coupling, emphasizing the distinction between “fast” and “slow” nuclear degrees of freedom in determining “self-trapping” and “self-localization” of exciton-polarons. Next, we discuss ultrafast intrachain exciton decoherence caused by exciton-phonon entanglement, which leads to fluorescence depolarization on the timescale of 10-fs. Interactions of the polymer with its environment causes the stochastic relaxation and localization of high-energy delocalized excitons onto chromophores. The coupling of excitons with torsional modes also leads to various dynamical processes. On sub-ps timescales it causes exciton-polaron formation (i.e., exciton localization and local polymer planarization). Conversely, on post-ps timescales stochastic torsional fluctuations cause exciton-polaron diffusion along the polymer chain and at higher temperatures to transient exciton delocalization via extended exciton states. We next describe a first-principles, Förster-type model of interchain exciton transfer and diffusion in the condensed phase, whose starting point is a realistic description of the donor and acceptor chromophores. Finally, we discuss condensed phase transient exciton delocalization in highly-ordered nanofibers. We survey experimental results and explain how they can be understood in terms of our theoretical description of exciton dynamics coupled to information on polymer multiscale structures. The review also contains a brief critique of computational methods to simulate exciton dynamics.

The CsSnBr3 photodetectors are fabricated by thermal evaporation and 75 °C in situ annealing, and the effect of in situ annealing on the morphology, structure, exciton dynamics and photoresponse of thermally evaporated CsSnBr3 films are investigated. Especially, temperature dependent steady-state photoluminescence (PL) and transient PL decaying have been analyzed in details for understanding the exciton dynamics. Meanwhile, effect of annealing on the activation energy for trap sites (E a), exciton binding energy (E b), activation energy for interfacial trapped carriers (Î" E), trap densities and carriers mobilities are studied and the annealed (A-CsSnBr3) reveals obviously lower E b and trap density together with notably higher carrier mobility than those of the unannealed (UA-CsSnBr3). Temperature dependence of the integrated PL intensity can be ascribed to the combining effect of the exciton dissociation, exciton quenching through trap sites and thermal activation of trapped carriers. The temperature dependent transient PL decaying analysis indicates that the PL decaying mechanism at low and high temperature is totally different from that in intermediate temperature range, in which combing effect of free exciton and localized state exciton decaying prevail. The beneficial effects of the in situ annealing on the photoresponse performance of the CsSnBr3 films can be demonstrated by the remarkable enhancement of the optimal responsivity (R) after in situ annealing which increases from less than 1 A Wâˆ'1 to 1350 A Wâˆ'1 as well as dramatically improved noise equivalent power, specific detectivity D * and Gain (G). [ABSTRACT FROM AUTHOR]

Light-emitting diodes (LEDs) based on perovskite materials are a new group of devices that are currently undergoing rapid development. A significant fraction of these devices is based on quasi-2D perovskites fabricated with large organic cations. In this work, we describe the ultrafast scale dynamics in a quasi-2D PEA2(Rb0.6Cs0.4)2Pb3Br10 perovskite material with an excess of RbBr, which was previously used to fabricate blue-emitting perovskite LEDs. The results obtained using transient absorption spectroscopy are consistent with the assumption that the carrier dynamics in this material are dominated by excitons, most of which decay by exciton–exciton annihilation when high-intensity excitation is used. Furthermore, a slow energy transfer between different quasi-2D domains taking place within 50 ps was observed. The content of the RbBr did not show any strong influence on the observed dynamics. Our results show that the exciton–exciton annihilation proceeds much faster in thin (n = 2) quasi-2D domains than in thick (n ≥ 4) domains. This finding implies that perovskites with high-n, quasi-2D domains are preferable for efficient perovskite lasers and bright perovskite LEDs. [ABSTRACT FROM AUTHOR]

The incorporation of singlet fission (SF) chromophores in solar cells is expected to bring significant increases in the power conversion efficiency thanks to multiexciton generation. However, efficient charge generation in the device is determined by the energy level alignment (ELA) between the active materials, which should favor exciton transport and separation under illumination. By combining ultraviolet photoemission spectroscopy and optical differential reflectance measurements, we determine the ELA in a prototypical SF heterojunction between pentacene (Pc) and perylene-tetracarboxylic-diimide (PTCDI) grown on Ag(111). Time-resolved X-ray photoelectron spectroscopy on such a system reveals light-induced modifications of the ELA; by measuring the transient shift of the core level photoemission lines we observe an accumulation of long-lived holes in the PTCDI within the first hundred picoseconds after the optical pump.

The effect of lattice fluctuations and electronic excitations on the radiative rate is demonstrated in CdSe/CdS core/shell spherical quantum dots (QDs). Using a combination of time-resolved photoluminescence spectroscopy and atomistic simulations, we show that lattice fluctuations can change the radiative rate over the temperature range from 78 to 300 K. We posit that the presence of the core/shell interface plays a significant role in dictating this behavior. We show that the other major factor that underpins the change in radiative rate with temperature is the presence of higher energy states corresponding to electron excitation into the shell. These effects should be present in other core/shell samples and should also affect other excited state rates, such as the rate of Auger recombination or the rate of charge transfer.

Triplet–triplet annihilation (TTA) up‐conversion is an effective way to utilize triplet excitons in organic light‐emitting diodes (OLEDs). However, the parameters characterizing the triplet excitons and relevant TTA process in OLEDs under working conditions have not been quantified. Here, an in situ method is established to map these parameters for further ascertaining their impact on device efficiency. The physical parameters, including triplet recombination rate, TTA rate, typical current JTTA, and saturated ratio, can be in situ quantified by transient electroluminescence technique. The expression of JTTA shows that minimizing the triplet quenching and maximizing the TTA rate are effective ways to lower JTTA. While highly efficient devices require a lower JTTA. Guided by these criteria, the device efficiency is promoted by weakening the triplet quenching via blending two materials. These investigations establish an in situ method to quantify the physical parameters that allow identifying the useful TTA materials and optimizing the design of device structures. [ABSTRACT FROM AUTHOR]

Doping transition metal impurities in semiconductor quantum dots (QDs) has been shown to offer an effective handle over their electronic, optical and magnetic properties. Incorporation of more than one type of transition ions in same QDs is nontrivial due to different thermodynamic constraints, however, it can provide attractive properties and insights to meet recent challenges in the field of luminescent and magnetic materials. Herein, we present a solution‐processed controlled synthesis of Mn and Ni codoped CdS colloidal QDs which show dual emission due to two different impurities. Controlled doping helps to understand the decay dynamics of exciton through various decay channels. Based on the competition between Mn and Ni dopant states, we observe reliable signatures for the short‐lived transient charge transfer of the photogenerated hole to the excited state of Mn and then to the Ni state. Along with the interesting excitonic dynamics, we also observe significant enhancement of magnetization due to the codoping. [ABSTRACT FROM AUTHOR]

Perovskite semiconductor nanocrystals have emerged as a promising family of materials for optoelectronic applications including light-emitting diodes, lasers, light-to-electricity convertors and quantum light emitters. The performances of these devices are fundamentally dependent on different aspects of the excited-state dynamics in nanocrystals. Herein, we summarize the recent progress on the photoinduced carrier dynamics studied by a variety of time-resolved spectroscopic methods in perovskite nanocrystals. We review the dynamics of carrier generation, recombination and transport under different excitation densities and photon energies to show the pathways that underpin the photophysics for light-emitting diodes and solar cells. Then, we highlight the up-to-date spin dynamics and coherent exciton dynamics being manifested with the exciton fine levels in perovskite semiconductor nanocrystals which are essential for potential applications in quantum information technology. We also discuss the controversial results and the possible origins yet to be resolved. In-depth study toward a comprehensive picture of the excited-state dynamics in perovskite nanocrystals may provide the key knowledge of the device operation mechanism, enlighten the direction for device optimization and stimulate the adventure of new conceptual devices.

Two-dimensional (2D) transition metal dichalcogenide (TMD) has emerged as an effective optoelectronics material due to its novel optical properties. Understanding the role of defects in exciton kinetics is crucial for achieving high-efficiency TMD devices. Here, we observe defects induced anomalous power dependence exciton dynamics and spatial distribution in hexagonal heterogeneous WS2. With transient absorption microscopy study, we illustrate that these phenomena originate from the competition between radiative and defect-related non-radiative decays. To understand the physics behind this, a decay model is introduced with two defect-related channels, which demonstrates that more excitons decay through non-radiative channels in the dark region than the bright region. Our work reveals the mechanisms of anomalous exciton kinetics by defects and is instrumental for understanding and exploiting excitonic states in emerging 2D semiconductors. [ABSTRACT FROM AUTHOR]

The experimental observation of long-lived quantum coherence in the excitation energy transfer (EET) process of the several photosynthetic light-harvesting complexes at low and room temperatures has aroused hot debate. It challenges the common perception in the field of complicated pigment molecular systems and evokes considerable theoretical efforts to seek reasonable explanations. In this work, we investigate the coherent exciton dynamics of the phycoerythrin 545 (PE545) complex. We use the dissipation equation of motion to theoretically investigate the effect of the local pigment vibrations on the population transfer process. The result indicates that the realistic local pigment vibrations do assist the energy transmission. We demonstrate the coherence between different pigment molecules in the PE545 system is an essential ingredient in the EET process among various sites. The coherence makes the excitation energy delocalized, which leads to the redistribution of the excitation among all the chromophores in the steady state. Furthermore, we investigate the effects of the complex high-frequency spectral density function on the exciton dynamics and find that the high-frequency Brownian oscillator model contributes most to the exciton dynamic process. The discussions on the local pigment vibrations of the Brownian oscillator model suggest that the local heterogeneous protein environments and the effects of active vibration modes play a significant role in coherent energy transport. [ABSTRACT FROM AUTHOR]