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.

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.

Perovskite nanoplatelets (NPLs) show great potential for high-color-purity light-emitting diodes (LEDs) due to their narrow line width and high exciton binding energy. However, the performance of perovskite NPL LEDs lags far behind perovskite quantum dot-/film-based LEDs, owing to their material instability and poor carrier transport. Here, we achieved efficient and stable pure blue-emitting CsPbBr3 NPLs with outstanding optical and electrical properties by using an aromatic ligand, 4-bromothiophene-2-carboxaldehyde (BTC). The BTC ligands with thiophene groups can guide two-dimensional growth and inhibit out-of-plane ripening of CsPbBr3 NPLs, which, meanwhile, increases their structural stability via strongly interacting with PbBr64- octahedra. Moreover, aromatic structures with delocalized π-bonds facilitate charge transport, diminish band tail states, and suppress Auger processes in CsPbBr3 NPLs. Consequently, the LEDs demonstrate efficient and color-stable blue emissions at 465 nm with a narrow emission line width of 17 nm and a maximum external quantum efficiency (EQE) of 5.4%, representing the state-of-the-art CsPbBr3 NPL LEDs.

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.

CVD grown monolayer MoS2films on c-sapphire substrates are vacuum annealed and capped with (111) NiO epitaxial films using pulsed laser deposition technique. Time, energy and polarization resolved optical techniques are used to understand the effect of capping on the excitonic properties of the monolayer MoS2. It has been observed that trion contribution in the photoluminescence (PL) spectra increases after the capping, suggesting an enhancement of electron concentration in the conduction band. This has been attributed to the capping driven reduction of physisorbed air molecules from the sulphur vacancy (VS) sites. Note that the air molecules act as passivating agents for theVS-donors. Low temperature polarization resolved PL spectroscopy and ultrafast pump and probe transient absorption spectroscopy (TAS) show an increase of the biexcitonic population in the system after the encapsulation. The TAS study further reveals longer lifetime for both A and B excitons in capped samples implying a reduction of non-radiative recombination rate of the excitons after the capping. It has also been observed that in the capped samples,K/K\'valleys are populated with trions under sufficiently high pump powers. This has been attributed to the lower non-radiative recombination rates of the high energy photoexcited carriers and the faster transfer of either electrons or holes from the high energy pockets to theK/K\'valleys. The study further reveals different many-body effects in excitons and trions.

The triplet-triplet annihilation (TTA) ratio and the rate coefficient (kTT) of TTA are key factors in estimating the contribution of triplet excitons to radiative singlet excitons in fluorescent TTA organic light-emitting diodes. In this study, deep learning models are implemented to predict key factors from transient electroluminescence (trEL) data using new numerical equations. A new TTA model is developed that considers both polaron and exciton dynamics, enabling the distinction between prompt and delayed singlet decays with a fundamental understanding of the mechanism. In addition, deep learning models for predicting the kinetic coefficients and TTA ratio are established. After comprehensive optimization inspired by photophysics, determination coefficient values of 0.992 and 0.999 are achieved in the prediction of kTT and TTA ratio, respectively, indicating a nearly perfect prediction. The contribution of each kinetic parameter of polaron and exciton dynamics to the trEL curve is discussed using various deep-learning models.

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.

Twisted van der Waals heterostructures show intriguing interface exciton physics, including hybridization effects and emergence of moiré potentials. Recent experiments have revealed that moiré-trapped excitons exhibit remarkable dynamics, where excited states show lifetimes that are several orders of magnitude longer than in monolayers. The origin of this behavior is still under debate. Based on a microscopic many-particle approach, we investigate the phonon-driven relaxation cascade of nonequilibrium moiré excitons in the exemplary MoSe2-WSe2 heterostructure. We track exciton relaxation pathways across different moiré mini-bands and identify the phonon-scattering channels assisting the spatial redistribution of excitons into low-energy pockets of the moiré potential. We unravel a phonon bottleneck in the flat band structure at low twist angles preventing excitons from fully thermalizing into the lowest state, explaining the measured enhanced emission intensity and lifetime of excited moiré excitons. Overall, our work provides important insights into exciton relaxation dynamics in flat-band exciton materials.

Creating hierarchical molecular block heterostructures, with the control over size, shape, optical, and electronic properties of each nanostructured building block can help develop functional applications, such as information storage, nanowire spectrometry, and photonic computing. However, achieving precise control over the position of molecular assemblies, and the dynamics of excitons in each block, remains a challenge. In the present work, the first fabrication of molecular heterostructures with the control of exciton dynamics in each block, is demonstrated. Additionally, these heterostructures are printable and can be precisely positioned using Direct Ink Writing-based (DIW) 3D printing technique, resulting in programable patterns. Singlet excitons with emission lifetimes on nanosecond or microsecond timescales and triplet excitons with emission lifetimes on millisecond timescales appear simultaneously in different building blocks, with an efficient energy transfer process in the heterojunction. These organic materials also exhibit stimuli-responsive emission by changing the power or wavelength of the excitation laser. Potential applications of these organic heterostructures in integrated photonics, where the versatility of fluorescence, phosphorescence, efficient energy transfer, printability, and stimulus sensitivity co-exist in a single nanowire, are foreseen.

The van der Waals (vdW) heterostructures composed of two-dimensional (2D) transition metal dichalcogenides (TMDs) and organic semiconductors demonstrate numerous compelling optoelectronic properties. However, the influence of the vdW epitaxial effect and temperature on the optoelectronic properties and interface exciton dynamics of heterostructures remains unclear. This study systematically investigates the fluorescence properties of TiOPc/WSe2 heterostructure. Comprehensive spectral characterization elucidates that the emission behavior of the TiOPc/WSe2 heterostructure arises from charge/energy transfer at the heterostructure interfaces and the structural ordering of the organic layer on the 2D monolayer WSe2 induced by vdW epitaxy. The interface exciton dynamic features probed by ultrafast transient spectroscopy reveal that the face-to-face molecular stacking configuration of TiOPc exhibits ultrafast exciton dynamics. In particular, we observe picosecond-scale absorption of organic molecular dimer cations, providing direct evidence of interface charge transfer at room temperature. Moreover, energy transfer from the TiOPc to WSe2 may exist based on the tunability in the fluorescence emission of the TiOPc/WSe2 heterostructure as the temperature changes. This study unveils the critical role of vdW epitaxy and temperature in the exciton dynamics of organic/2D TMDs hybrid systems and provides guidance for studying interlayer charge and energy transfer in organic/inorganic heterostructures.