Chirality of CsPbBr3 Nanocrystals with Varying Dimensions in the Presence of Chiral Molecules.

Chiral lead halide perovskite (LHP) nanocrystals (NCs) have been attracting considerable interest for circularly polarized luminescence (CPL)-based optoelectronic applications. This study combined experimental and computational analyses to investigate how the dimensionality of 3D (cubic) to 0D (quantum dots) influences the tunable chiral emission of CsPbBr3 LHP NCs. The circular dichroism (CD) spectra have a significant blue shift from 508 to 406 nm. The dissymmetry factors for CD (gCD) change from ±2.5 × 10-3 to ±7.5 × 10-3 as dimensionality varies from 3D to 0D in the presence of the chiral molecule (cyclohexylethylamine, CHEA). A significant luminescence dissymmetry factor (glum) of ±5.6 × 10-4 is observed in the 0D CsPbBr3 NCs. Theoretical calculations using structural distortion parameters, the extent of charge transfer, and electrostatic potential profiles have revealed that the most significant enhancement of the chirality transfer occurs from the CHEA molecules to 0D NCs, and the order of chirality transfer from CHEA to CsPbBr3 NCs is 0D (quantum dots) > 2D (nanoplatelet) > 3D (cubic).

Evidence of Energy and Hole Transfer between 2D CdSe0.7Te0.3 Alloy NPLs with Porphyrin Molecules.

Colloidal two-dimensional (2D) nanoplatelets (NPLs) have been extensively studied owing to promising potential in optoelectronic applications. Here, we have reported the preparation of 2D CdSeTe alloy NPLs and investigated their energy and charge transfer with porphyrin molecules. The red shifting in the optical properties suggests the change in the band gaps. Furthermore, the energy and the charge transfer are evident in the composite of CdSeTe alloy NPLs with 5,10,15,20-tetra(4pyridyl)-porphyrin (TpyP) molecules. The quenching in the photoluminescence (PL) spectra and PL decay time supports the energy transfer (~61 % efficiency) and the charge transfer. The thermodynamically feasible hole transfer is evidenced by the band alignment of the alloy NPLs and TpyP molecules, which is further supported by a transient absorption spectroscopy (TAS) study. The TA study found the hole transfer within ~3 ps time scale, proving the effective charge carrier separation for better optoelectronic applications.

Introducing Ag Dopants into CdSe Nanoplatelets (NPLs) Leads to Effective Charge Separation for Better Photodetector Performance.

Solution-processed colloidal cadmium chalcogenide nanoplatelets (NPLs)-based photodetectors (PD) are promising materials for next-generation optoelectronic devices due to their excellent optical properties. Here, we report on ultrafast carrier relaxation dynamics of four monolayer (4 ML) Ag-doped CdSe (Ag: CdSe) NPLs using ultrafast transient absorption spectroscopy and their photodetectors applications. A broad dopant emission is observed at around 650 nm with a large FWHM of ~431 meV and band edge emission at 515 nm. The intragap dopant state acts as a hole acceptor, which leads to better charge separation. The ultrafast transient absorption spectroscopy study shows faster carrier recombination dynamics with a hole transfer time scale of ~10 ps in Ag-doped CdSe NPLs. This supports the excited hole capture phenomenon at the dopant state. Ag-doped CdSe NPLs-based PD performed better than undoped CdSe NPLs with detectivity and responsivity values of 1.3×1010 Jones and 2.4 mA/W, respectively.

Insights of the efficient hydrogen evolution reaction performance in bimetallic Au4Cu2 nanoclusters.

The design of efficient electrocatalysts for improving hydrogen evolution reaction (HER) performance using atomically precise metal nanoclusters (NCs) is an emerging area of research. Here, we have studied the HER electrocatalytic performance of monometallic Cu6 and Au6 nanoclusters and bimetallic Au4Cu2 nanoclusters. A bimetallic Au4Cu2/MoS2 composite exhibits excellent HER catalytic activity with an overpotential (η10) of 155 mV vs. reversible hydrogen electrode observed at 10 mA cm-2 current density. The improved HER performance in Au4Cu2 is due to the increased electrochemically active surface area (ECSA), and Au4Cu2 NCs exhibits better stability than Cu6 and Au6 systems and bare MoS2. This augmentation offers a greater number of active sites for the favorable adsorption of reaction intermediates. Furthermore, by employing X-ray photoelectron spectroscopy (XPS) and Raman analysis, the kinetics of HER in the Au4Cu2/MoS2 composite were elucidated, attributing the favorable performance to better electronic interactions occurring at the interface between Au4Cu2 NCs and the MoS2 substrate. Theoretical analysis reveals that the inherent catalytic enhancement in Au4Cu2/MoS2 is due to favorable H atom adsorption over it and the smallest ΔGH* value. The downshift in the d-band of the Au4Cu2/MoS2 composite influences the binding energy of intermediate catalytic species. This new catalyst sheds light on the structure-property relationship for improving electrocatalytic performance at the atomic level.

Copper Nanoclusters as Multienzymes Mimic Activities of Oxidase and Ascorbic Acid Oxidase in the Presence of Imidazole.

Artificial nanoenzymes based on metal nanoclusters have received great attention for multienzyme activities nowadays. In this work, pepsin-capped copper NCs (Cu-Pep NCs) are used as oxidase, ascorbic acid oxidase (AAO), and peroxidase mimics, and their activities are enhanced by the introduction of imidazole. The oxidase activity increased almost 7.5-fold, while 5-fold and 2-fold increases were observed for the peroxidase and AAO-like activity, respectively. The enhanced radical formation in the presence of imidazole moieties facilitates the enzymatic activity of the Cu-Pep-NCs/Imid system. This work describes the different enzymatic activities of the NCs, paving a new way for artificial nanoenzymes having enhanced activities.

Probing the Fluorescence Intermittency of Bimetallic Nanoclusters using Single-Molecule Fluorescence Spectroscopy.

Single-molecule spectroscopy (SMS) is a unique and competent technique to study molecule dynamics and sense biomolecules precisely. The design of an ultrahigh-stability single fluorophore probe with excellent photostability and long-lived dark transient states for single-molecule fluorescence microscopy is challenging. Here, we found that the photostability of bimetallic AuAg28 nanoclusters is better than monometallic Ag29 nanoclusters. The photon antibunching experiments unveiled exceptional brightness and remarkable photostability with high survival times of up to 218 s with minimal blinking. AuAg28 NCs exhibited longer "on" times and shorter "off" times as compared to Ag29 NCs. The statistical analysis was performed on at least 100 molecules that showed single-step photobleaching and almost a 5-fold enhancement in intensity on Au doping in Ag29 NCs. The distinctive and tunable photophysics of metal NCs can offer huge potential in pushing single-molecule dynamic measurements to be carried out biologically.

Impacts of Exciton Binding Energy and Dielectric Confinement of Layered Lead Halide Perovskites on Carrier Relaxation and Exciton Phonon Interactions.

This work highlights the significance of dielectric confinements and exciton binding energy of hybrid layered perovskites (LPs) in controlling the carrier relaxation dynamics of LPs for designing efficient optoelectronic devices. The polarizability of organic spacer cations in LPs modulates the carrier-phonon and carrier-carrier interactions, which eventually control the carrier relaxation dynamics. Here, we have varied the alkyl-ammonium chain length in the LPs to change the dielectric confinement, and the first-principles calculations reveal that the long-chain organic spacer experiences stronger dielectric confinement in comparison to short-chain organic spacer cation-based LPs. Transient absorption spectroscopic analysis suggests that the larger dielectric confinement and higher exciton binding energy exhibit faster carrier relaxation dynamics. The enhanced exciton-phonon interaction leads to faster carrier relaxation dynamics. The much softer phonon modes are responsible for the higher up-conversion of acoustic modes to optical modes, which leads to slower carrier relaxation dynamics in n-butylamine (BA) based LPs.

Transition Metal Ions Influence the Performance of Photodetector of Two-Dimensional CdS Nanoplatelets.

Transition metal-doped two-dimensional (2D) semiconductor nanoplatelets (NPLs) with atomically precise thickness have attracted much research interest due to their inherent photo-physical properties. In this work, we have synthesized 2D Cu-doped CdS NPLs, investigated the charge transfer dynamics using ultrafast transient absorption spectroscopy, and fabricated an efficient photodetector device. A large Stoke's shifted emission at ~685 nm with an average lifetime of about ~1.45 µs is observed in Cu-doped CdS NPLs. Slower bleach recovery kinetics leads to large charge carrier separation in Cu-doped NPLs which is beneficial for photodetector applications. Cu-doped NPLs-based photodetectors exhibit high photocurrent, fast response (~120 ms), ~600 times higher photoresponsivity, and ~300 times higher detectivity (~4.1×1013 Jones) than undoped CdS NPLs. These excellent properties of Cu-doped CdS NPLs make this material an efficient alternative for next-generation optoelectronic devices.

Electron Transfer Dynamics from CsPbBr3 Nanocrystals to Au144 Clusters.

Lead halide perovskite nanocrystals have received significant attention as an absorber material for designing efficient optoelectronic devices. The fundamental understanding of the hot carrier (HC) dynamics as well as its extraction in hybrid systems is essential to further boost the performance of solar cells. Herein, we have explored the electron transfer dynamics in the CsPbBr3-Au144 cluster hybrid using ultrafast transient absorption spectroscopy. Our analysis reveals faster HC cooling time (from 515 to 334 fs) and a significant drop in HC temperature from 1055 to 860 K in hybrid, suggesting the hot electron transfer from CsPbBr3 nanocrystals to the Au nanoclusters (NCs). Eventually, we observe a much faster hot electron transfer compared to the band-edge electron transfer, and 45% hot-electron transfer efficiency was achieved at 0.64 eV, above band-edge photoexcitation. Furthermore, the significant enhancement of the photocurrent to the dark current ratio in this hybrid system confirms the charge separation via the electron transfer from CsPbBr3 nanocrystals to Au144 NCs. These findings on HC dynamics could be beneficial for optoelectronic devices.

Experimental and computational insights into luminescence in atomically precise bimetallic Au6-nCun(MPA)5 (n = 0-2) clusters.

Bimetallic nanoclusters (NCs) have emerged as a new class of luminescent materials for potential applications in sensing, bio-imaging, and light-emitting diodes (LEDs). Here, we have synthesized gold-copper bimetallic nanoclusters (AuCu NCs) using a one-step co-reduction method and tuned the emission wavelength from 520 nm to 620 nm by changing the [Cu2+]/[Au3+] molar ratio. The quantum yield (QY) increases from 6% to 13% upon incorporation of the Cu atom in the Au NCs. MALDI-TOF mass spectrometric analysis reveals that the composition of the Au NCs is Au6(MPA)5, and the bimetallic nanocluster is Au4Cu2(MPA)5, where 3-mercaptopropionic acid (MPA) is used as the capping ligand. Furthermore, we investigated the optimized structures of the as-synthesized NCs using density functional theory (DFT) along with analysis of the preferable adsorption sites using Fukui functions. We report the HOMO-LUMO gap, which is consistent with the experimentally observed red shift in the UV-Vis absorption features of the Au NCs upon copper doping. XPS studies suggest the formation of intermixing of states between the 5d orbitals of Au and the 3d orbitals of Cu in the AuCu NCs after incorporating Cu atoms into the Au NCs, which is corroborated by the DFT calculations on electronic charge transfer from the Cu to the Au atom in the NCs. The coupling between Au(I) and Cu(I) facilitates the formation of a low-lying mixed Au(I)-Cu(I) energy state. This study elaborates on the impact of Cu doping on the excited-state relaxation dynamics of AuCu NCs.

Unraveling the Effect of Single Atom Doping on the Carrier Relaxation Dynamics of MAg24n- Nanoclusters.

Precisely doped metal nanoclusters (NCs) are currently emerging nanomaterials for their unique photophysical properties. Here, we report the influence of single atom doping on the excited state relaxation dynamics of a series of MAg24(2,4-Me2PhS)18n- NCs where M is Ag, Au, Pd, and Pt. The NCs with a group 11 metal (Ag and Au) as central atoms exhibit dual emission at NIR and visible range, whereas it shows only NIR emission for group 10 metal (Pd and Pt) doped NCs. Global target analyses of transient absorption (TA) data reveal the three-state relaxation, i.e., initially excited state (Sn), ligand-centered charge transfer (CT) state (SL), and metal-centered lowest excited state (S1). Apart from the HOMO-LUMO (H-L) energy gap, the electron affinity of the central metal atom and rigidity of the NC structural framework influence the relaxation processes of the NCs. The extensive study into the relaxation dynamics will bestow the single atomic level modulation of photophysical properties.

Modulating the Carrier Relaxation Dynamics in Heterovalently (Bi3+) Doped CsPbBr3 Nanocrystals.

Manipulation of intrinsic carrier relaxation is crucial for designing efficient lead halide perovskite nanocrystal (NC) based optoelectronic devices. The influence of heterovalent Bi3+ doping on the ultrafast carrier dynamics and hot carrier (HC) cooling relaxation of CsPbBr3 NCs has been studied using femtosecond transient absorption spectroscopy and first-principles calculations. The initial HC temperature and LO phonon decay time point to a faster HC relaxation rate in the Bi3+-doped CsPbBr3 NCs. The first-principles calculations disclose the acceleration of carrier relaxation in Bi3+-doped CsPbBr3 NCs due to the appearance of localized bands (antitrap states) within the conduction band. The higher Born effective charges (Z*) and higher soft energetic optical phonon density of states cause higher electron-phonon scattering rates in the Bi-doped CsPbBr3 system, which is responsible for the faster HC cooling rate in doped systems.

Self-Assembled Metal Nanoclusters: Driving Forces and Structural Correlation with Optical Properties.

Studies on self-assembly of metal nanoclusters (MNCs) are an emerging field of research owing to their significant optical properties and potential applications in many areas. Fabricating the desired self-assembly structure for specific implementation has always been challenging in nanotechnology. The building blocks organize themselves into a hierarchical structure with a high order of directional control in the self-assembly process. An overview of the recent achievements in the self-assembly chemistry of MNCs is summarized in this review article. Here, we investigate the underlying mechanism for the self-assembly structures, and analysis reveals that van der Waals forces, electrostatic interaction, metallophilic interaction, and amphiphilicity are the crucial parameters. In addition, we discuss the principles of template-mediated interaction and the effect of external stimuli on assembly formation in detail. We also focus on the structural correlation of the assemblies with their photophysical properties. A deep perception of the self-assembly mechanism and the degree of interactions on the excited state dynamics is provided for the future synthesis of customizable MNCs with promising applications.

Role of Ligand on Photophysical Properties of Nanoclusters with fcc Kernel: A Case Study of Ag14(SC6H4X)12(PPh3)8 (X = F, Cl, Br).

The structure-property correlation of a series of silver nanoclusters (NCs) is essential to understand the origin of photophysical properties. Here, we report a series of face-centered cubic (fcc)-based silver NCs by varying the halogen atom in the thiolate ligand to investigate the influence of the halide atoms on the electronic structure. These are {Ag14(FBT)12(PPh3)8·(solvent)x} (NC-1), Ag14(CBT)12(PPh3)8 (NC-2), and Ag14(BBT)12(PPh3)8 (NC-3), where 4-fluorothiophenol (FBT), 4-chlorothiophenol (CBT), and 4-bromothiophenol (BBT) have been utilized as thiolate ligands, respectively. Interestingly, the optical and electrochemical bandgap values of these NCs nicely correlated with the electronic effect of the halides, which is governed by the intracluster and interclusters π-π interactions. These clusters are emissive at room temperature and the luminescence intensity increases with the lowering of temperature. The short lifetime data suggest that the emission is predominantly originating due to the interband relaxation (d → sp) of the Ag cores. Femtosecond transient absorption (TA) spectra revealed similar types of decay profiles for NC-2 and NC-3 and longer decay time for NC-2. The relaxation dominates the decay profile to the surface states and most of the excited-state energy dissipates via this process. This supports the molecular-like dynamics of these series of NCs with an fcc core. This overview shed light on an in-depth understanding of ligand's role in luminescence and transient absorption spectra.

Deciphering the Relaxation Mechanism of Red-Emitting Carbon Dots Using Ultrafast Spectroscopy and Global Target Analysis.

Red-emitting carbon dots (C-dots) have tremendous potential for bioimaging and optoelectronic applications. Here, we investigated the structural modification of red-emitting C-dots due to boron doping and their ultrafast relaxation dynamics. It is evident from the X-ray photoelectron spectroscopy study that the relative percentage of pyrridinic nitrogen is increased at the expense of amino nitrogen and graphitic nitrogen in B-doped C-dots. Transient absorption spectroscopy and global target analysis reveal the formation of an additional excited-state level that takes away a significant amount of the excited-state population after boron doping. This new excited state slows the initial relaxation process toward the emissive state from 317 to 750 fs and increases the overall lifetime from 1.03 to 1.45 ns in B-doped C-dots.

Implications of relaxation dynamics of collapsed conjugated polymeric nanoparticles for light-harvesting applications.

Conjugated polymer-based nanostructures have been explored extensively from energy harvesting to healthcare applications due to their unique photophysical properties. This perspective includes the mechanism of the formation of polymer nanoparticles from linear chain polymers by utilizing experimental and theoretical studies. Conjugated polymer nanoparticles lead to changes in excitonic absorption bands, photoluminescence (PL) bands, and relaxation kinetics due to the inter-chain interactions between the chromophoric sub-units and the formation of the low-lying delocalized collective state. Here, we have illustrated the current understanding of the ultrafast relaxation dynamics of π-conjugated polymer-based nanostructured materials using global and target analysis. We have shown the impacts of the photoinduced carrier dynamics of polymer nanoparticles on the energy and charge transfer processes. Polymer nanoparticles found promising applications in bio-imaging, photothermal and photodynamic therapeutic agents, photocatalysis, and lasing materials. Finally, we have given the future perspectives of luminescent polymer nanoparticles.

The Impact of Aggregation of Quaterthiophenes on the Excited State Dynamics.

Oligothiophenes and their aggregates play a dominant role in optoelectronic and light-harvesting applications. Here, we controlled the degree of aggregation of 2,2':5',2″:5'',2‴-quaterthiophene (QTH) to shed light on the impact of the aggregation on the excited state dynamics. QTH aggregation realized the control over the Intersystem Crossing (ISC) rates and, in turn, the formation of triplet excited states via the simple addition of water to QTH solutions in THF. From global target analysis, the time scale was 345.5 ps for ISC for QTHs in THF, but it was 2.33 ns in the case of QTH solutions featuring 70% water. Notably, the excitonic coupling between closely packed QTHs occurred predominantly in the aggregates formed in the presence of large water concentrations. Relaxation dynamics of the resulting QTH-aggregates differed substantially from QTH solutions at lower water content. For example, QTH-aggregates lacked any triplet excited states, and the unusual emission occurs from lower excitonic states from these predominantly H-aggregates.

One-Dimensional Silver-Thiolate Cluster-Assembly: Effect of Argentophilic Interactions on Excited-State Dynamics.

We report the synthesis, crystal structure, and electronic structure calculations of a one-dimensional silver-thiolate cluster-assembled and its ultrafast spectroscopic investigation. Experiments and theory find the material to have a significant gap as the HOMO-LUMO absorption corresponds to 2.69 eV, and the defect-free structure is calculated to have a gap of 2.82 eV. Cluster models demonstrate that the gap energy is length-dependent. Theoretical studies identify a nonbonding metallophilic interaction that exists between two Ag atoms in adjacent strings that helps to stabilize the chain structure. Transient absorption spectroscopy reveals that the electron dynamics is a mixture of the behavior of cluster and nanoparticle, with the material having a 346 fs ground-state relaxation like a cluster, and the electron dynamics is dominated by electron-phonon coupling with a decay time of 1.5 ps, unlike the isolated cluster whose decay is mostly radiative.

Self-assembly of copper nanoclusters: isomeric ligand effect on morphological evolution.

Tailoring the hierarchical self-assembly of metal nanoclusters (NCs) is an emergent area of research owing to their precise structure and flexible surface environment. Herein, the morphological evolution from rods to platelets to ribbon-like structures through self-assembly of Cu7 NCs is dictated by the positional isomerism of the surface capping ligand, dimethylbenzenethiol (DMBT). Besides cuprophilic interaction, the interplay between π-π stacking and agostic interaction (Cu⋯H-C) directs the inter-NC organization into different ordered architectures. The excited-state relaxation dynamics of the red phosphorescent assembled structures has been correlated with their compactness and the degree of bonding interactions present.

Surface motifs regulated aggregation induced emission in gold-silver nanoclusters.

Aggregation-induced emission (AIE) is a recently developed strategy to design highly luminescent metal nanoclusters (NCs), which can be controlled by the surface motifs [M(i)-SR] of NCs. This communication is an account to understand the AIE in gold silver (AuAg) NCs, where the Au(i)-thiolate motif is engineered by doping different amount of Ag in Au NCs. Investigation revealed the great impact of Au(i)-thiolate motifs on the AIE of AuAg NCs.