Novel Au/Cu2NiSnS4 Nano-Heterostructure: Synthesis, Structure, Heterojunction Band Offset and Alignment, and Interfacial Charge Transfer Dynamics.

Considering the importance of physics and chemistry at material interfaces, we have explored the coupling of multinary chalcogenide semiconductor Cu2NiSnS4 nanoparticles (CNTS NPs) for the first time with the noble metal (Au) to form Au-CNTS nano-heterostructures (NHSs). The Au-CNTS NHSs is synthesized by a simple facile hot injection method. Synergistic experimental and theoretical approaches are employed to characterize the structural, optical, and electrical properties of the Au-CNTS NHSs. The absorption spectra demonstrate enhanced and broadened optical absorption in the ultraviolet-visible-near-infrared (UV-Vis-NIR) region, which is corroborated by cyclic voltammetry (CV) readings. CV measurements show type II staggered band alignment, with a conduction band offset (CBO) of 0.21 and 0.23 eV at the Au-CNTS/CdS and CNTS/CdS interface, respectively. Complementary first-principles density functional theory (DFT) calculations predict the formation of a stable Au-CNTS NHSs, with the Au nanoparticle transferring its electrons to the CNTS. Moreover, our interface analysis using ultrafast transient absorption experiments demonstrate that the Au-CNTS NHSs facilitates efficient transport and separation of photoexcited charge carriers when compared to pristine CNTS. The transient measurements further reveal a plasmonic electronic transfer from the Au nanoparticle to CNTS. Our advanced analysis and findings will prompt investigations into new functional materials and their photo/electrocatalysis and optoelectronic device applications in the future.

Size-Tunable Manganese-Doped Spheroidal CsPbCl3 Quantum Dots.

Manganese doping has been demonstrated as a versatile tool to tune the emission of CsPbCl3 nanocrystals (NCs). Although this has been demonstrated in nanocubes and nanoplatelets, strategies for doping Mn2+ in size-tunable, excitonic CsPbCl3 quantum dots (QDs) remain absent. In this work, we demonstrate the synthesis of size-tunable spheroidal CsPbCl3:Mn2+ QDs, which can be obtained by a water-hexane interfacial combined anion and cation exchange strategy starting from CsPbBr3 QDs. Interestingly, the QDs exhibit a fast 0.2 ms Mn2+ photoluminescence (PL) lifetime and an energy transfer (ET) time of approximately 100 ps from the excitonic state of the QD to the atomic state of the Mn2+ ion. The size dependence observation of the manganese PL efficiency and the slow ET rate suggest that Mn2+ mainly gets incorporated at the QD's surface, highlighting the importance of strategies chosen for the incorporation of Mn2+ into perovskite QDs.

Reversible CsPbBr3 ↔ CsPb2Br5 Transformation via Reverse Micellar Aqueous Solution.

Lead halide perovskites suffer from water and moisture instability due to the highly ionic nature of the crystal structures, though a few groups took advantage of it for chemical transformation via water-assisted strategy. However, direct exposure of the perovskite to bulk water leads to uncontrolled chemical transformation. Here, we report a controlled chemical transformation of CsPbBr3 to CsPb2Br5 triggered by nanoconfined water by placing CsPbBr3 in the nonpolar phase within a reverse micelle. The chemical transformation reaction is probed by using steady-state and time-resolved optical spectroscopy. We observe absorption and photoluminescence in the UV region stemming clearly from the CsPb2Br5 phase upon interaction with the reverse micellar aqueous solution. Transmission electron microscopy and X-ray diffraction measurements further provided the structure and morphology. Our results direct the formation of CsPbBr3-CsPb2Br5 nanocomposite under dry conditions while the chemically transformed CsPb2Br5 phase exists only in moist conditions, which we explain via the CsBr-stripping mechanism.

A Bound Exciton Resonance Modulated by Bulk and Localized Coherent Phonons in Double Perovskites.

Optically excited electronic excitations are coupled to the soft and polar halide perovskite lattice, generating coherent phonons after subpicosecond interband laser-excitation. In Ag-based halide double perovskites, Ag-vacancies can bind free excitons, resulting in a pronounced bound exciton resonance. Here, we report the detection of three modulation frequencies corresponding to coherent phonons in Ag-based double perovskite nanocrystals at distinct spectral positions at the bound exciton resonance. Two of them are found in oscillatory spectral shifts of the bound exciton resonance and are identified as Cs- and Br-related bulk phonons. Surprisingly, a third frequency is observed as an intensity modulation. We argue that this amplitude oscillation is a consequence of an optically generated vibronic wave packet localized at a Ag-vacancy. Consequently, the localized coherent phonon modulates the giant oscillator strength of the bound exciton. This optically induced and spatially localized lattice shaking could potentially be useful for initiating photochemical reactions with atomic precision.

CuInS2-Decorated Perovskite Nanoarchitecture: Halide-Driven Energy and Electron Transfer.

Perovskite nanocrystals (NCs) are an emergent and game-changing entrant in semiconductor research, yet the research on the corresponding nanoheterostructures remains in its infancy. In this work, we fabricate a type II nanoarchitecture of CsPbX3 NCs (where X = Cl, Br, or I) and CuInS2 quantum dots to investigate the energy and charge transfer (ET and CT, respectively) processes. Optical measurements of CsPbX3/CuInS2 show efficient photoluminescence (PL) quenching when X = Br or I, while the PL quenching efficiency of the X = Cl compound is 2 orders of magnitude lower. We argue the drastic PL quenching in the X = I compound is solely due to the CT process, while for the X = Br compound, a predominantly ET process is active. In contrast to the driving force (-ΔG) for the CT process, we observe the reverse order of the electron transfer process, for which we propose the electron transfer occurs in the Marcus inverted region. Our halide-dependent controlled regulation of CT and ET processes in these nanoarchitectures may find promising optoelectronic applications.

Obtaining Ligand-Free Aqueous Au-Nanoparticles Using Reversible CsPbBr3 ↔ Au@CsPbBr3 Nanocrystal Transformation.

Water-hexane interfacial preparation of photostable Au@CsPbBr3 (Au@CPB) hybrid nanocrystals (NCs) from pure CsPbBr3 (CPB) NCs is reported, with the coexistence of exciton and localized surface plasmon resonance with equal dominance. This enables strong exciton-plasmon coupling in these plasmonic perovskite NCs where not only the photoluminescence is quenched intrinsically due to ultrafast charge separation, but also the light absorption property increases significantly, covering the entire visible region. Using a controlled interfacial strategy, a reversible chemical transformation between CPB and Au@CPB NCs is shown, with the simultaneous eruption of larger-size ligand-free aqueous Au nanoparticles (NPs). An adsorption-desorption mechanism is proposed for the reversible transformation, while the overgrowth reaction of the Au NPs passes through the Au aggregation intermediate. This study further shows that the plasmonic Au@CPB hybrid NCs as well as ligand-free Au NPs exhibit clear surface enhanced Raman scattering (SERS) effect of a commercially available probe molecule. Overall, the beautiful interfacial chemistry delivers two independent plasmonic materials, i.e., Au@CPB NCs and ligand-free aqueous Au NPs, which may find important implications in photocatalytic and biomedical applications.

Stimulating Phonon Bottleneck Effect in Organic Semiconductors by Charge-Transfer-Mediated J-Aggregation.

Hot carriers rapidly lose kinetic energies on a subpicosecond time scale, posing significant limitations on semiconductors' photon-conversion efficiencies. To slow the hot carrier cooling, the phonon bottleneck effect is constructed prevalently in quantum-confined structures with discrete energy levels. However, the maximum energy separation (ΔEES) between the energy levels is in a range of several hundred meV, leading to unsatisfactory cooling time. To address this, we design a novel organic semiconductor capable of forming intermolecular charge transfer (CT) in J-aggregates, where the lowest singlet excited state (S1) splits into two states due to the significant interplay between the Coulomb interaction and intermolecular CT coupling. The ΔEES between the two states can be adjusted up to 1.02 eV, and an extremely slow carrier cooling process of ∼72.3 ps was observed by femtosecond transient absorption spectroscopy. Moreover, the phonon bottleneck effect was identified in organic materials for the first time, and CT-mediated J-aggregation with short-range interactions was found to be the key to achieving large ΔEES. The significantly prolonged carrier cooling time, compared to <100 fs in the isolated molecule (10-6 M), highlights the potential of organic molecules with diversified aggregation structures in achieving long-lived hot carriers. These findings provide valuable insights into the intrinsic photophysics of electron-phonon scattering in organic semiconductors.

Breaking AgInTe2 Quantum Dot Chain to Fabricate AgInTe2-ZnS Janus Nanocrystals.

Colloidal multinary chalcogenides (MnCs) have emerged as excellent optoelectronic materials, where S- and Se-based MnCs show considerable progress; however, the Te counterpart suffers from detrimental surface oxidation. Moreover, Te-based I-III-VI MnCs (e.g., AgInTe2) tend to form a one-dimensional (1-D) anisotropic structure via the self-assembly of surface-oxidized Te, thus restricting the isolation of AgInTe2 quantum dots (QDs). We report successful control of the self-assembly of Te-based MnCs to arrest the growth of AgInTe2 QDs by using a synergistic capping agent (dodecanethiol and oleic acid). The reaction proceeds with several intermediates, including hexagonal microrods (MR), tetragonal QDs in a chain arrangement, and tetragonal MRs. Importantly, we note that the incorporation of ZnS QDs triggers the breaking of the chain arrangement of the AgInTe2 QDs and the emergence of evenly distributed AgInTe2-ZnS Janus nanocrystals with significantly reduced long-term Te-oxidative properties. Arresting the AgInTe2 QD chain and the subsequent Janus nanocrystal formation could have promising opportunities for 1-D charge hopping and efficient charge transport for optoelectronic applications, respectively.

Interfacial band offset engineering with barium-doping towards enhanced performance of all inorganic CsPbI2Br perovskite solar cells.

This study investigates the incorporation of Ba2+ at a low concentration into CsPbI2Br, resulting in the formation of mixed CsPb1-xBaxI2Br perovskite films. Photovoltaic devices utilizing these Ba-doped CsPbI2Br (Ba-CsPbI2Br) perovskite films achieved a higher stabilized power conversion efficiency of 14.07% compared to 11.60% for pure CsPbI2Br films. First-principles density functional theory calculations indicate that the improved device performance can be attributed to the efficient transport of conduction electrons across the interface between Ba-CsPbI2Br and the TiO2 electron transporting layer (ETL). The Ba-CsPbI2Br/TiO2 interface exhibits a type-II staggered band alignment with a smaller conduction band offset (CBO) of 0.25 eV, in contrast to the CsPbI2Br/TiO2 interface with a CBO of 0.48 eV. The reduced CBO at the Ba-CsPbI2Br/TiO2 interface diminishes the barrier for conduction electrons to transfer from the Ba-CsPbI2Br layer to the TiO2 layer, facilitating efficient charge transport.

Giant Exciton Stokes Shift in Interfacially Prepared Cs(Mn/Pb)Cl3 Alloy Nanoplatelets.

Controlling the reabsorption of light by an emitting material is one of the keys to improving the performance of light-emitting devices. We prepare a set of size-dependent Cs(Mn/Pb)Cl3 alloy nanoplatelets (NPls) with substantial enhancement in the exciton Stokes shift, reducing the light-reabsorption significantly. We perform interfacial Mn-alloying using a shuttling ligand that transports MnCl2 from aqueous to nonaqueous phase and delivers it to NPls. While the exciton Stokes shift in 2-5 monolayer (ML) CsPbBr3 NPls rises from 20 to 108 meV, the exciton Stokes shift increases drastically up to 600 meV in 2 ML Cs(Mn/Pb)Cl3 NPls and further reduces upon increasing the thickness. Moreover, the exciton PL peak in the Mn-alloy NPls remains unperturbed by the quantum-confinement effect. A model based on the interplay between Mn2+/Mn3+ during the charge transfer process is proposed, accounting for such a large exciton Stokes shift. Finally, we utilize the large exciton Stokes-shifted alloy NPls for successful demonstration of white-light generation.

Simultaneous Hydrogen Generation and Exciplex Stimulated Emission in Photobasic Carbon Dots.

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps-to-ns timescales, is much faster than proton delivery (∼µs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady-state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four-level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.

Silver nanoparticle enhanced metal-organic matrix with interface-engineering for efficient photocatalytic hydrogen evolution.

Integrating plasmonic nanoparticles into the photoactive metal-organic matrix is highly desirable due to the plasmonic near field enhancement, complementary light absorption, and accelerated separation of photogenerated charge carriers at the junction interface. The construction of a well-defined, intimate interface is vital for efficient charge carrier separation, however, it remains a challenge in synthesis. Here we synthesize a junction bearing intimate interface, composed of plasmonic Ag nanoparticles and matrix with silver node via a facile one-step approach. The plasmonic effect of Ag nanoparticles on the matrix is visualized through electron energy loss mapping. Moreover, charge carrier transfer from the plasmonic nanoparticles to the matrix is verified through ultrafast transient absorption spectroscopy and in-situ photoelectron spectroscopy. The system delivers highly efficient visible-light photocatalytic H2 generation, surpassing most reported metal-organic framework-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic nanoparticles and organic semiconductors.

Halide-Driven Halogen-Hydrogen Bonding versus Chelation in Perovskite Nanocrystals: A Concept of Charge Transfer Bridging.

The choice of surface functionalized ligands to encapsulate semiconductor nanocrystals (NCs) is important for tailoring their optoelectronic properties. We use a small bidentate 8-hydroxyquinoline (HQ) molecule to surface functionalize CsPbX3 perovskite NCs (X = Cl, Br, I), along with traditional long-chain monodentate ligands. Our experimental results using optical and ultrafast spectroscopy depict a halogen-hydrogen bonding formation in the HQ functionalized CsPbCl3 and CsPbBr3 NCs, which act as a charge transfer (CT) bridging for the interfacial hole transfer from the NCs to the HQ molecule as fast as 540 fs. In contrast, weak chelation is observed for HQ-coupled CsPbI3 NCs without an active CT process. We explain two distinct surface coupling mechanisms via the polarizability of halides and larger PbI64- octahedral cage size. Control of two contrasting halide-dependent surface coupling phenomena of a small molecule that further regulate the CT process may have significant implications in their development in optoelectronics.

Chemical coupling of halide perovskite nanocrystals with a metal quinolate complex for white light generation.

Herein we report the construction of a white light emitting (WLE) nanocomposite by chemically coupling halide perovskite nanocrystals (HPNCs; e.g., orange-emitting Mn2+-doped CsPbCl3) with a metal quinolate complex (e.g., a cyan-emitting calcium quinolate (CaQ2) complex) while keeping their distinct features. The surface chloride of HPNCs coupled with the Ca-metal center of the CaQ2 complex without altering the morphology, size, and dopant oxidation state of the HPNCs and provided additional environmental stability of the WLE nanocomposite. The photostable solid WLE nanocomposite displays chromaticity of (0.33, 0.32), color rendering index (CRI) of 80, correlated color temperature (CCT) of 5483 K, and quantum yield of 54.1%. This clearly indicates their bright WLE nature with properties close to those of bright midday sunlight. The current work will bring new surface chemistry between HPNCs and inorganic complexes and new paradigm toward advanced light emitting applications.

Water-Triggered Chemical Transformation of Perovskite Nanocrystals.

Recently emerged lead-halide perovskite nanocrystals (PNCs) are promising optoelectronic material due to their easy solution processability, wide range of color tunability, as well as very high photoluminescence quantum yield. Despite their significant success in lab-scale optoelectronic applications, the long-term stability becomes the main issue, hindering them towards commercialization. The highly ionic nature of such lead-halide structure makes them extremely unstable in water and air. But a very few groups have taken the advantage of such nature of the crystal structure for water-triggered chemical transformation towards shape, composition, and morphology controlled stable and bright PNCs, which are otherwise difficult to obtain by typical direct approach. Furthermore, using polymer as an encapsulating layer for the PNCs, water-soluble stable PNCs have been prepared. In this review, the recent progress on the water-hexane interface chemistry towards chemical transformation to produce several PNCs is described. Such method not only ensure to yield several shape-controlled perovskites nanocrystals, but also formation of perovskites in aqueous phase that show promising application towards bio-imaging.

Confined Excitons in Spherical-Like Halide Perovskite Quantum Dots.

Quantum dots (QDs) offer unique physical properties and novel application possibilities like single-photon emitters for quantum technologies. While strongly confined III-V and II-VI QDs have been studied extensively, their complex valence band structure often limits clear observations of individual transitions. In recently emerged lead-halide perovskites, band degeneracies are absent around the bandgap reducing the complexity of optical spectra. We show that for spherical-like CsPbBr3 QDs with diameters >6 nm, excitons confine with respect to their center-of-mass motion leading to well-pronounced resonances in their absorption spectra. Optical pumping of the lowest-confined exciton with femtosecond laser pulses not only bleaches all excitons but also reveals a series of distinct induced absorption resonances which we attribute to exciton-to-biexciton transitions and are red-shifted by the biexciton binding energy (∼40 meV). The temporal dynamics of the bleached excitons further support our exciton confinement model. Our study provides the first insight into confined excitons in CsPbBr3 QDs and gives a detailed understanding of their linear and nonlinear optical spectra.

Ultrafast proton transfer of the aqueous phenol radical cation.

Proton transfer (PT) reactions are fundamental to numerous chemical and biological processes. While sub-picosecond PT involving electronically excited states has been extensively studied, little is known about ultrafast PT triggered by photoionization. Here, we employ femtosecond optical pump-probe spectroscopy and quantum dynamics calculations to investigate the ultrafast proton transfer dynamics of the aqueous phenol radical cation (PhOH˙+). Analysis of the vibrational wave packet dynamics reveals unusually short dephasing times of 0.18 ± 0.02 ps and 0.16 ± 0.02 ps for the PhOH˙+ O-H wag and bend frequencies, respectively, suggestive of ultrafast PT occurring on the ∼0.1 ps timescale. The reduced potential energy surface obtained from ab initio calculations shows that PT is barrierless when it is coupled to the intermolecular hindered translation between PhOH˙+ and the proton-acceptor water molecule. Quantum dynamics calculations yield a lifetime of 193 fs for PhOH˙+, in good agreement with the experimental results and consistent with the PT reaction being mediated by the intermolecular O⋯O stretch. These results suggest that photoionization can be harnessed to produce photoacids that undergo ultrafast PT. In addition, they also show that PT can serve as an ultrafast deactivation channel for limiting the oxidative damage potential of radical cations.

Interfacial Manganese-Doping in CsPbBr3 Nanoplatelets by Employing a Molecular Shuttle.

Mn-doping in cesium lead halide perovskite nanoplatelets (NPls) is of particular importance where strong quantum confinement plays a significant role towards the exciton-dopant coupling. In this work, we report an immiscible bi-phasic strategy for post-synthetic Mn-doping of CsPbX3 (X=Br, Cl) NPls. A systematic study shows that electron-donating oleylamine acts as a shuttle ligand to transport MnX2 through the water-hexane interface and deliver it to the NPls. The halide anion also plays an essential role in maintaining an appropriate radius of Mn2+ and thus fulfilling the octahedral factor required for the formation of perovskite crystals. By varying the thickness of parent NPls, we can tune the dopant incorporation and, consequently, the exciton-to-dopant energy transfer process in doped NPls. Time-resolved optical measurements offer a detailed insight into the exciton-to-dopant energy transfer process. This new approach for post-synthetic cation doping paves a way towards exploring the cation exchange process in several other halide perovskites at the polar-nonpolar interface.

Phenolic compounds and extracts from Crotalaria calycina Schrank potentially alleviate pain and inflammation through inhibition of cyclooxygenase-2: An in vivo and molecular dynamics studies.

Crotalaria calycina Schrank is a local Bangladeshi plant well-accepted by the tribal population for its medicinal properties. The primary approach of our study was to uncover the analgesic and anti-inflammatory potential of methanol extract of C. calycina stem in mice model with in silico molecular docking and molecular dynamics simulation approach. Phenolic compounds were identified and quantified from the extract through high-performance liquid chromatography-diode array detector (HPLC-DAD) analysis. Writhing assay through injection of acetic acid, licking assay through formalin injection, and finally, hot plate assay was employed to observe the analgesic activity. The carrageenan-induced paw edema model was employed to determine the anti-inflammatory potential of the extract. In silico molecular docking and molecular dynamics were also run to validate the in vivo study results. Eight polyphenolic compounds from the extract were identified and quantified via HPLC-DAD analysis, and (-) epicatechin was most abundantly distributed (87.15 ± 0.24 mg/100 g dry extract). In vivo study revealed that 400 mg/kg dose significantly inhibited (P < 0.01) the writhing response in the writhing assay and demonstrated the highest percent of inhibition of licking (70.67%) in the late part of the licking test. The same extract dose produced the highest (74.71%) percent of maximal effect (% MPE) in the hot plate assay. It demonstrated the highest percent of edema inhibition (68.00%) in the fourth hour of the paw edema assay. Molecular docking and molecular dynamics simulation of (-) epicatechin, caffeic acid, and kaempferol with cyclooxygenase-2 revealed that they have similar interactions to the standard inhibitor celecoxib. These valuable bioactive compounds may induce significant analgesic and anti-inflammatory properties in MECCS. Therefore, based on the findings of this study, it can be concluded that C. calycina stem can be a prospect in the medicinal field due to its remarkable analgesic and anti-inflammatory effect.

Observation of intra- and intermolecular vibrational coherences of the aqueous tryptophan radical induced by photodetachment.

The study of the photodetachment of amino acids in aqueous solution is pertinent to the understanding of elementary processes that follow the interaction of ionizing radiation with biological matter. In the case of tryptophan, the tryptophan radical that is produced by electron ejection also plays an important role in numerous redox reactions in biology, although studies of its ultrafast molecular dynamics are limited. Here, we employ femtosecond optical pump-probe spectroscopy to elucidate the ultrafast structural rearrangement dynamics that accompany the photodetachment of the aqueous tryptophan anion by intense, ∼5-fs laser pulses. The observed vibrational wave packet dynamics, in conjunction with density functional theory calculations, identify the vibrational modes of the tryptophan radical, which participate in structural rearrangement upon photodetachment. Aside from intramolecular vibrational modes, our results also point to the involvement of intermolecular modes that drive solvent reorganization about the N-H moiety of the indole sidechain. Our study offers new insight into the ultrafast molecular dynamics of ionized biomolecules and suggests that the present experimental approach can be extended to investigate the photoionization- or photodetachment-induced structural dynamics of larger biomolecules.