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.

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.

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.

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.

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.

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.

Investigation of Morphology-Controlled Ultrafast Relaxation Processes of Aggregated Porphyrin.

Here, we have synthesized rod and flake shaped morphology of porphyrin aggregates from 5, 10, 15, 20-tetra (4-n-octyloxyphenyl) porphyrin (4-opTPP) molecule which are evident from scanning electron microscopy (SEM). The formation of J-type aggregation is evident from steady state and time-resolved fluorescence spectroscopic studies. Ultrafast transient absorption spectroscopic studies reveal that the excited state lifetime is controlled by the morphology and the time constant for S1→S0 relaxation changes from 3.05 ps to 744 ps with changing the shape from rod to flake, respectively. In spite of similar exciton coupling energy in both the aggregates, the flake shaped aggregates undergo a faster exciton relaxation process and the non-radiative relaxation channels are found to depend on the shape of aggregates. The fundamental understanding of morphology controlled ultrafast relaxation processes of aggregated porphyrin is important for designing efficient light harvesting devices.

Global and target analysis of relaxation processes of the collapsed state of P3HT polymer nanoparticles.

Organic-inorganic heterostructure materials have received significant research interest for designing light harvesting devices because of their efficient charge separation. Here, we design organic and inorganic nano-heterostructures using conjugated polymer nanoparticles (PNPs) [poly(3-hexylthiophene-2,5-diyl), P3HT] and Au nanoparticles. We investigate the carrier relaxation processes of this heterostructure at different time scales by ultrafast transient absorption spectroscopy. The lifetime of the singlet state (S1) of the pristine polymer shortens from 480.7 ps to 2.8 ps due to the formation of nanoparticles, and the formation of a delocalized collective state (CLS) is obtained in polymer nanoparticles whose lifetime is found to be 384.6 ps. The hot and ultrafast electron transfers occur from P3HT polymer nanoparticles to Au nanoparticles and the time constants are 253 fs and 37.7 ps, respectively, which are responsible for the efficient charge separation in such heterostructures. Such a fundamental study of relaxation processes of organic-inorganic nano heterostructures is very significant for designing light harvesting systems.

Nanoscale Strategies for Light Harvesting.

Recent advances and the current status of challenging light-harvesting nanomaterials, such as semiconducting quantum dots (QDs), metal nanoparticles, semiconductor-metal heterostructures, π-conjugated semiconductor nanoparticles, organic-inorganic heterostructures, and porphyrin-based nanostructures, have been highlighted in this review. The significance of size-, shape-, and composition-dependent exciton decay dynamics and photoinduced energy transfer of QDs is addressed. A fundamental knowledge of these photophysical processes is crucial for the development of efficient light-harvesting systems, like photocatalytic and photovoltaic ones. Again, we have pointed out the impact of the metal-nanoparticle-based surface energy transfer process for developing light-harvesting systems. On the other hand, metal-semiconductor hybrid nanostructures are found to be very promising for photonic applications due to their exciton-plasmon interactions. Potential light-harvesting systems based on dye-doped π-conjugated semiconductor polymer nanoparticles and self-assembled structures of π-conjugated polymer are highlighted. We also discuss the significance of porphyrin-based nanostructures for potential light-harvesting systems. Finally, the future perspective of this research field is given.

Opportunities and challenges in energy and electron transfer of nanocluster based hybrid materials and their sensing applications.

This feature article highlights the recent advances of luminescent metal nanoclusters (MNCs) for their potential applications in healthcare and energy-related materials because of their high photosensitivity, thermal stability, low toxicity, and biocompatibility. Current studies reveal that metal cluster based hybrid systems could pave the way for energy harvesting and sensing applications. To begin with, we illustrate general synthesis methodologies for atomically precise metal nanoclusters and discuss the origin of photoluminescence properties and the electronic transitions of nanoclusters. Successively, we discuss the energy transfer and electron transfer processes in metal cluster based hybrid systems with CdTe QDs, carbon dots (C-dots), functionalized DNA and graphene oxide. Finally, we address the potential advantages of metal clusters and their hybrid systems as an optical probe for the selective detection of toxic metal ions. A tentative outlook on fundamental challenges and future opportunities of this research field is highlighted.

Ultrafast carrier dynamics in 2D-2D hybrid structures of functionalized GO and CdSe nanoplatelets.

Considerable attention has been paid to designing graphene based 2D hybrid nanostructures for their potential applications in various areas from healthcare to energy harvesting. Herein, we have prepared 2D-2D hybrid structures of 2D CdSe nanoplatelets (NPLs) with thiol (-SH) functionalized reduced graphene oxide (G-Ph-SH). Microscopic and spectroscopic studies reveal that the G-Ph-SH surface is successfully decorated by CdSe NPLs through a thiophenol (-SH) linker. The significant photoluminescence quenching (65%) and the shortening of decay time from 1 ns to 0.4 ns of CdSe NPLs are observed after adding 100 µg of G-Ph-SH. Furthermore, the femto-second transient absorption spectroscopic (fs-TAS) study reveals that the growth time of CdSe NPLs in the composite is reduced to 0.4 ps from 0.8 ps due to faster hot electron cooling. A faster component of 1.4 ps in the kinetic parameters of the composite system further suggests that the ultrafast electron transfer occurs from the conduction band of CdSe NPLs to surface functionalized reduced graphene oxide. This type of 2D-2D hybrid structure may open up new possibilities in light harvesting applications.

Influence of shape on the carrier relaxation dynamics of CsPbBr3 perovskite nanocrystals.

Lead halide perovskite nanocrystals (NCs) have recently emerged as a new class of functional materials for designing efficient light harvesting systems because of their unique photophysical properties. Here, we report the influence of different shapes on the relaxation dynamics of perovskite nanocrystals. The structural transformation of CsPbBr3 NCs from cubic shape to rod shape occurs by changing the solvent from toluene to dichloromethane (DCM). Rietveld analysis reveals that the crystallinity along with the preferred orientation (PO) of the orthorhombic phase plays a vital role for the unidirectional growth of rod shaped CsPbBr3 NCs in DCM. Time-resolved emission spectroscopy and ultrafast transient absorption spectroscopy are used to understand the photoinduced relaxation processes. Global and target analysis of femto-second transient absorption kinetics has been done to understand the individual excited-state species. The analysis reveals that trap states play an important role in the carrier relaxation dynamics of cubic and rod shaped NCs. The lifetime of the shallow trap (ST) changes from 25 ps to 45 ps and the lifetime of the deep trap (DT) state changes from 163 ps to 303 ps with changing the shape of the nanocrystals from cubic to rod. This work highlights the tuning of the crystal phase, shape and the exciton dynamics of CsPbBr3 NCs that would be beneficial for designing efficient photovoltaic devices.

Recent Advances on the Optical Properties of Eu3+ Ion in Nano-Systems.

Rare-earth (RE) doped nanomaterials have already proven promising materials for advanced materials and technologies including optics, lasers, catalysts, alloys, magnets, electronics, lighting, bioanalyses, imaging etc. because of their outstanding properties such as extremely narrow emission bands, long lifetimes, large strokes shifts, photostability and absence of blinking. The efficient of RE doped phosphors is found to be controlled by tuning nonradiative relaxation pathway which eventually controls by tuning crystal phase of host, lattice vibration, concentration of dopant etc. Cross relaxation nonradiative decay due to concentration quenching can be manipulated by controlling dopant concentration. This review article highlights the optical properties of Eu3+ ion in various hosts such as fluoride, phosphate, silica, semiconductor, oxyhalide, vanadate, molybdate and tungstate because of its importance for potential applications. It is important to know how the host environment influences the radiative and nonradiative relaxation which eventually controls the overall photoluminescence properties. Of particular attention is how the optical properties of Eu3+ ion vary with changing the host environment with the anticipation that such knowledge will permit us to construct efficient nanomaterials. Finally, a tentative outlook on future advances of this research field is given.

Light Harvesting and Photocurrent Generation in a Conjugated Polymer Nanoparticle-Reduced Graphene Oxide Composite.

Polymer-graphene nanocomposites are promising candidates for light harvesting applications such as photocatalysis and photovoltaics, where significant charge separation occurs due to photoinduced electron transfer. Much attention has been paid to using reduced graphene oxide (r-GO) as template for anchoring various nanomaterials due to its efficient electron accepting and transport properties. Here, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) nanoparticles are prepared from MEH-PPV polymer and the change in photophysical properties upon formation of polymer nanoparticles (PNPs) from the molecular state are investigated by using steady-state and time-resolved spectroscopy. Nanocomposites are constructed by adding hexadecylamine-functionalized positively charged MEH-PPV PNPs to a solution of negatively charged r-GO. Steady-state and time-resolved spectroscopy are also used to study the electronic interactions between PNPs and r-GO. Ultrafast femtosecond up-conversion and transient absorption spectroscopy unequivocally confirms the electron transfer process from the excited state of MEH-PPV PNPs to r-GO at the interface of the nanocomposite. Analysis reveals that the charge separation time is found to be pulse-width-limited (<100 fs). Due to charge separation in these nanocomposites, an increase (2.6 fold) of photocurrent under visible light illumination is obtained. The fundamental understanding of the charge transfer dynamics affords new opportunities to design efficient light-harvesting systems based on inorganic-organic hybrids.

Light Harvesting and White-Light Generation in a Composite of Carbon Dots and Dye-Encapsulated BSA-Protein-Capped Gold Nanoclusters.

Several strategies have been adopted to design an artificial light-harvesting system in which light energy is captured by peripheral chromophores and it is subsequently transferred to the core via energy transfer. A composite of carbon dots and dye-encapsulated BSA-protein-capped gold nanoclusters (AuNCs) has been developed for efficient light harvesting and white light generation. Carbon dots (C-dots) act as donor and AuNCs capped with BSA protein act as acceptor. Analysis reveals that energy transfer increases from 63 % to 83 % in presence of coumarin dye (C153), which enhances the cascade energy transfer from carbon dots to AuNCs. Bright white light emission with a quantum yield of 19 % under the 375 nm excitation wavelength is achieved by changing the ratio of components. Interesting findings reveal that the efficient energy transfer in carbon-dot-metal-cluster nanocomposites may open up new possibilities in designing artificial light harvesting systems for future applications.

Efficient White-Light Generation from Ionically Self-Assembled Triply-Fluorescent Organic Nanoparticles.

Low cost, simple, and environmentally friendly strategies for white-light generation which do not require rare-earth phosphors or other toxic or elementally scare species remain an essentially unmet challenge. Progress in the area of all-organic approaches is highly sought, single molecular systems remaining a particular challenge. Taking inspiration from the designer nature of ionic-liquid chemistry, we now introduce a new strategy toward white-light emission based on the facile generation of nanoparticles comprising three different fluorophores assembled in a well-defined stoichiometry purely through electrostatic interactions. The building blocks consist of the fluorophores aminopyrene, fluorescein, and rhodamine 6G which represent blue, green, and red-emitting species, respectively. Spherical nanoparticles 16(±5) nm in size were prepared which display bright white-light emission with high fluorescence quantum efficiency (26 %) and color coordinate at (0.29, 0.38) which lie in close proximity to pure white light (0.33, 0.33). It is noteworthy that this same fluorophore mixture in free solution yields only blue emission. Density functional theory calculations reveal H-bond and ground-state proton transfer mediated absolute non-parallel orientation of the constituent units which result in frustrated energy transfer, giving rise to emission from the individual centers and concomitant white-light emission.

Photoswitching and Thermoresponsive Properties of Conjugated Multi-chromophore Nanostructured Materials.

Conjugated multi-chromophore organic nanostructured materials have recently emerged as a new class of functional materials for developing efficient light-harvesting, photosensitization, photocatalysis, and sensor devices because of their unique photophysical and photochemical properties. Here, we demonstrate the formation of various nanostructures (fibers and flakes) related to the molecular arrangement (H-aggregation) of quaterthiophene (QTH) molecules and their influence on the photophysical properties. XRD studies confirm that the fiber structure consists of >95% crystalline material, whereas the flake structure is almost completely amorphous and the microstrain in flake-shaped QTH is significantly higher than that of QTH in solution. The influence of the aggregation of the QTH molecules on their photoswitching and thermoresponsive photoluminescence properties is revealed. Time-resolved anisotropic studies further unveil the relaxation dynamics and restricted chromophore properties of the self-assembled nano/microstructured morphologies. Further investigations should pave the way for the future development of organic electronics, photovoltaics, and light-harvesting systems based on π-conjugated multi-chromophore organic nanostructured materials.

Lanthanide-doped nanocrystals: strategies for improving the efficiency of upconversion emission and their physical understanding.

The fundamental understanding of lanthanide-doped upconverted nanocrystals remains a frontier area of research because of potential applications in photonics and biophotonics. Recent studies have revealed that upconversion luminescence dynamics depend on host crystal structure, size of the nanocrystals, dopant concentration, and core-shell structures, which influence site symmetry and the distribution and energy migration of the dopant ions. In this review, we bring to light the influences of doping/co-doping concentration, crystal phase, crystal size of the host, and core-shell structure on the efficiency of upconversion emission. Furthermore, the lattice strain, due to a change in the crystal phase and by the core-shell structure, strongly influences the upconversion emission intensity. Analysis suggests that the local environment of the ion plays the most significant role in modification of radiative and nonradiative relaxation mechanisms of overall upconversion emission properties. Finally, an outlook on the prospects of this research field is given.

Multichromophoric organic molecules encapsulated in polymer nanoparticles for artificial light harvesting.

We designed a self-assembled multichromophoric organic molecular arrangement inside polymer nanoparticles for light-harvesting antenna materials. The self-assembled molecular arrangement of quaterthiophene molecules was found to be an efficient light-absorbing antenna material, followed by energy transfer to Nile red (NR) dye molecules, which was confined in polymer nanoparticles. The efficiency of the antenna effect was found to be 3.2 and the effective molar extinction coefficient of acceptor dye molecules was found to be enhanced, which indicates an efficient light-harvesting system. Based on this energy-transfer process, tunable photo emission and white light emission has been generated with 14 % quantum yield. Such self-assembled oligothiophene-NR systems encapsulated in polymer nanoparticles may open up new possibilities for fabrication of artificial light harvesting system.

Influence of size and shape on the photocatalytic properties of SnO2 nanocrystals.

Tuning the functional properties of nanocrystals is an important issue in nanoscience. Here, we are able to tune the photocatalytic properties of SnO2 nanocrystals by controlling their size and shape. A structural analysis was carried out by using X-ray diffraction (XRD)/Rietveld and transmission electron microscopy (TEM). The results reveal that the number of oxygen-related defects varies upon changing the size and shape of the nanocrystals, which eventually influences their photocatalytic properties. Time-resolved spectroscopic studies of the carrier relaxation dynamics of the SnO2 nanocrystals further confirm that the electron-hole recombination process is controlled by oxygen/defect states, which can be tuned by changing the shape and size of the materials. The degradation of dyes (90%) in the presence of SnO2 nanoparticles under UV light is comparable to that (88%) in the presence of standard TiO2 Degussa P-25 (P25) powders. The photocatalytic activity of the nanoparticles is significantly higher than those of nanorods and nanospheres because the effective charge separation in the SnO2 nanoparticles is controlled by defect states leading to enhanced photocatalytic properties. The size- and shape-dependent photocatalytic properties of SnO2 nanocrystals make these materials interesting candidates for photocatalytic applications.