In-situ growth of low-dimensional perovskite-based insular nanocrystals for highly efficient light emitting diodes.

Regulation of perovskite growth plays a critical role in the development of high-performance optoelectronic devices. However, judicious control of the grain growth for perovskite light emitting diodes is elusive due to its multiple requirements in terms of morphology, composition, and defect. Herein, we demonstrate a supramolecular dynamic coordination strategy to regulate perovskite crystallization. The combined use of crown ether and sodium trifluoroacetate can coordinate with A site and B site cations in ABX3 perovskite, respectively. The formation of supramolecular structure retard perovskite nucleation, while the transformation of supramolecular intermediate structure enables the release of components for slow perovskite growth. This judicious control enables a segmented growth, inducing the growth of insular nanocrystal consist of low-dimensional structure. Light emitting diode based on this perovskite film eventually brings a peak external quantum efficiency up to 23.9%, ranking among the highest efficiency achieved. The homogeneous nano-island structure also enables high-efficiency large area (1 cm2) device up to 21.6%, and a record high value of 13.6% for highly semi-transparent ones.

Investigation of Ultrafast Configurational Photoisomerization of Bilirubin Using Femtosecond Stimulated Raman Spectroscopy.

Phototherapy is an efficient and safe way to reduce high levels of free 4Z,15Z-bilirubin (ZZ-BR) in the serum of newborns. The success of BR phototherapy lies in photoinduced configurational and structural isomerization processes that form excretable isomers. However, the physical picture of photoinduced photoisomerization of ZZ-BR is still unclear. Here, we strategically implement tunable femtosecond stimulated Raman spectroscopy and several time-resolved electronic spectroscopies, assisted by quantum chemical calculations, to dissect the detailed primary configurational isomerization dynamics of free ZZ-BR in organic solvents. The results of this study demonstrate that upon photoexcitation, ultrafast configurational isomerization proceeds by a volume-conserving "hula twist", followed by intramolecular hydrogen-bond distortion and large-scale rotation of the two dipyrrinone halves of the ZZ-BR isomer in a few picoseconds. After that, most of the population recovers back to ZZ-BR, and a very small amount is converted into stable BR isomers via structural isomerization.

Identification of Alkoxy Radicals as Hydrogen Atom Transfer Agents in Ce-Catalyzed C-H Functionalization.

The intermediacy of alkoxy radicals in cerium-catalyzed C-H functionalization via H-atom abstraction has been unambiguously confirmed. Catalytically relevant Ce(IV)-alkoxide complexes have been synthesized and characterized by X-ray diffraction. Operando electron paramagnetic resonance and transient absorption spectroscopy experiments on isolated pentachloro Ce(IV) alkoxides identified alkoxy radicals as the sole heteroatom-centered radical species generated via ligand-to-metal charge transfer (LMCT) excitation. Alkoxy-radical-mediated hydrogen atom transfer (HAT) has been verified via kinetic analysis, density functional theory (DFT) calculations, and reactions under strictly chloride-free conditions. These experimental findings unambiguously establish the critical role of alkoxy radicals in Ce-LMCT catalysis and definitively preclude the involvement of chlorine radical. This study has also reinforced the necessity of a high relative ratio of alcohol vs Ce for the selective alkoxy-radical-mediated HAT, as seemingly trivial changes in the relative ratio of alcohol vs Ce can lead to drastically different mechanistic pathways. Importantly, the previously proposed chlorine radical-alcohol complex, postulated to explain alkoxy-radical-enabled selectivities in this system, has been examined under scrutiny and ruled out by regioselectivity studies, transient absorption experiments, and high-level calculations. Moreover, the peculiar selectivity of alkoxy radical generation in the LMCT homolysis of Ce(IV) heteroleptic complexes has been analyzed and back-electron transfer (BET) may have regulated the efficiency and selectivity for the formation of ligand-centered radicals.

A Precipitation-Enhanced Emission (PEE) Strategy for Increasing the Brightness and Reducing the Liver Retention of NIR-II Fluorophores.

The lack of organic fluorophores with high quantum yields (QYs) and low liver retention in the second near-infrared (NIR-II) window has become a bottleneck in the bioimaging field. An approach to address these problems is proposed by encapsulating phosphorylated fluorescent dyes into biodegradable calcium phosphate nanoparticles. First, an NIR-II molecule, LJ-2P, is designed with increased water solubility by introducing two phosphate groups. Meanwhile, LJ-2P co-precipitates with calcium ions to form LJ-2P nanoparticles (NPs). The QYs of LJ-2P NPs in aqueous solution is increased by 36.57-fold to 5.12% compared with that of LJ-2P. This unique phenomenon is named as precipitation-enhanced emission (PEE), whose detailed mechanism is explored by femtosecond transient absorption. It is demonstrated that co-precipitation of LJ-2P with calcium ions changes the micro-environment, which restricts the molecular rotation and reduces the interaction of water molecules, especially the excited-state proton transfer. In addition, due to the pH-sensitive nature, more than 80% of the LJ-2P NPs are metabolized in the liver within 24 h. Based on the excellent optical properties and good biocompatibility, high-contrast vascular visualization and breast tumor detecting are achieved. This strategy can apply to other NIR-II fluorophores to achieve high QYs and low liver retention.

Observation of Ultrafast Interfacial Exciton Formation and Relaxation in Graphene/MoS2 Heterostructure.

Heterostructures constructed from graphene and transition metal dichalcogenides (TMDs) have established a new platform for optoelectronic applications. After a large number of studies, one intriguing debate is the existence of the interfacial exciton in graphene/TMDs. Hereby, by combined optical pump-terahertz probe spectroscopy and transient absorption spectroscopy, we report the observation of the interfacial exciton in graphene/MoS2 heterostructure. With the photon energy well below the band gap of monolayer MoS2, the hot electrons of graphene are transferred to MoS2 within 0.5 ps; subsequently, the relaxation of the holes in graphene and electrons in MoS2 shows an identical time scale of 15-18 ps, which manifests the formation and relaxation of the interfacial exciton in the heterostructure following photoexcitation. Moreover, a model of the carrier heating and photogating effect in graphene is proposed to estimate the amount of transferred charge, which agrees well with the experimental results. Our study provides insights into the dynamics of graphene-based heterostructure interfacial non-equilibrium carriers.

Schottky-type GaN-based UV photodetector with atomic-layer-deposited TiN thin film as electrodes.

In this work, a GaN-based UV photodetector with an asymmetric electrode structure was fabricated by atomic layer deposition (ALD) of TiN layers. The thickness of the TiN can be monitored in situ by a quartz crystal microbalance (QCM) and precisely controlled through the modulation of deposition cycles. During the ALD process, periodic variation in the QCM frequency was observed and correlated to the physical adsorption, chemical bonding, and the excessive precursor exhaust, which included tetrakis(dimethylamino)titanium (TDMAT) and N sources. The asymmetric TiN/GaN/TiN photodetector showed excellent photosensing performance, with a UV-visible rejection ratio of 173, a responsivity of 4.25 A/W, a detectivity of 1.1×1013 Jones, and fast response speeds (a rise time of 69 µs and a decay time of 560 µs). Moreover, the device exhibits high stability, with an attenuation of only approximately 0.5% after 360 nm light irradiation for 157 min. This result indicates the potential of TiN as a transparent contact electrode for GaN-based optoelectronic devices.

Tracking Ultrafast Structural Dynamics in a Dual-Emission Anti-Kasha-Active Fluorophore Using Femtosecond Stimulated Raman Spectroscopy.

The anti-Kasha process provides the possibility of using high-energy excited states to develop novel applications. Our previous research (Nature communications, 2020, 11, 793) has demonstrated a dual-emission anti-Kasha-active fluorophore for bioimaging application, which exhibits near-infrared emissions from the S1 state and visible anti-Kasha emissions from the S2 state. Here, we applied tunable blue-side femtosecond stimulated Raman spectroscopy (FSRS) and transient absorption spectroscopy, assisted by quantum calculations, to reveal the anti-Kasha dual emission mechanism, in which the emergence of two fluorescing states is due to the retardation of internal conversion from the S2 state to the S1 state. It has been demonstrated that the facts of anti-Kasha high-energy emission are commonly attributed to a large energy gap between the two excited states, leading to a decrease in the internal conversion rate due to a poor Franck-Condon factor. In this study, analysis of the calculation and FSRS experimental results provide us further insight into the dual-emission anti-Kasha mechanism, where the observation of hydrogen out-of-plane Raman modes from FSRS suggested that, in addition to the energy-gap law, the initial photoinduced molecular conformational change plays a key role in influencing the rate of internal conversion.