Krishna Kanta Haldar

Hybrid Colloidal Au-CdSe Pentapod Heterostructures Synthesis and their Photocatalytic Properties

In this report, we present a self-driven chemical process to design exclusive Au/CdSe pentapod heterostructures with Au core and CdSe arms. We have analyzed these heterostructures using high-resolution transmission electron microscope (HRTEM), high angle annular dark field-scanning transmission electron microscopic (HAADF-STEM), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) studies. Microscopic studies suggest that pentapod arms of CdSe are nucleated on the (111) facets of Au and linearly grown only along the [001] direction. From the XPS study, the shifting of peak positions in the higher binding energy region for Au/CdSe heterostructures compared to Au nanoparticles has been found which indicates the charge transfer from CdSe to Au in heterostructures. The steady state and time resolved spectroscopic studies unambiguously confirm the electron transfer from photoexcited CdSe to Au, and the rate of electron transfer is found to be 3.58×10⁸ s⁻¹. It is interesting to note that 87.2% of R6G dye is degraded by the Au/CdSe heterostructures after 150 min UV irradiation, and the apparent rate constant for Au/CdSe heterostructures is found to be 0.013 min⁻¹. This new class of metal-semiconductor heterostructures opens up new possibilities in photocatalytic, solar energy conversion, photovoltaic, and other new emerging applications.

Core-size-dependent catalytic properties of bimetallic Au/Ag core-shell nanoparticles.

Bimetallic core-shell nanoparticles have recently emerged as a new class of functional materials because of their potential applications in catalysis, surface enhanced Raman scattering (SERS) substrate and photonics etc. Here, we have synthesized Au/Ag bimetallic core-shell nanoparticles with varying the core diameter. The red-shifting of the both plasmonic peaks of Ag and Au confirms the core-shell structure of the nanoparticles. Transmission electron microscopy (TEM) analysis, line scan EDS measurement and UV-vis study confirm the formation of core-shell nanoparticles. We have examined the catalytic activity of these core-shell nanostructures in the reaction between 4-nitrophenol (4-NP) and NaBH4 to form 4-aminophenol (4-AP) and the efficiency of the catalytic reaction is found to be increased with increasing the core size of Au/Ag core-shell nanocrystals. The catalytic efficiency varies from 41.8 to 96.5% with varying core size from 10 to 100 nm of Au/Ag core-shell nanoparticles, and the Au100/Ag bimetallic core-shell nanoparticle is found to be 12-fold more active than that of the pure Au nanoparticles with 100 nm diameter. Thus, the catalytic properties of the metal nanoparticles are significantly enhanced because of the Au/Ag core-shell structure, and the rate is dependent on the size of the core of the nanoparticles.

Fluorescence enhancement and quenching of Eu3+ ions by Au–ZnO core-shell and Au nanoparticles

We investigate the enhancement and quenching of Eu3+ emission in presence of Au–ZnO core-shell nanoparticles and Au nanoparticles. The quenching of Eu3+-emission in presence of Au nanoparticles is caused by change of nonradiative rate due to energy transfer. However, the enhancement of Eu3+-emission in presence of Au–ZnO core-shell nanoparticles is due to local field, which modifies the radiative and nonradiative rate. Enhancement and quenching of Eu3+ emission reflect the change in environment of Eu3+ from Au nanoparticles to Au–ZnO core-shell nanoparticles which is confirmed by the Judd–Ofelt parameter (Ω2) analysis.

Formation of Heteroepitaxy in Different Shapes of Au–CdSe Metal–Semiconductor Hybrid Nanostructures

Formation of heteroepitaxy and designing different-shaped heterostructured nanomaterials of metal and semiconductor in solution remains a frontier area of research. However, it is evident that the synthesis of such materials is not straightforward and needs a selective approach to retain both metal and semiconductor identities in the reaction system during heterostructure formation. Herein, the epitaxial growth of semiconductor CdSe on selected facets of metal Au seeds is reported and different shapes (flower, tetrapod, and core/shell) hetero-nanostructures are designed. These results are achieved by controlling the reaction parameters, and by changing the sequence and timing for introduction of different reactant precursors. Direct evidence of the formation of heteroepitaxy between {111} facets of Au and (0001) of wurtzite CdSe is observed during the formation of these three heterostructures. The mechanism of the evolution of these hetero-nanostructures and formation of their heteroepitaxy with the planes having minimum lattice mismatch are also discussed. This shape-control growth mechanism in hetero-nanostructures should be helpful to provide more information for establishing the fundamental study of heteroepitaxial growth for designing new nanomaterials. Such metal-semiconductor nanostructures may have great potential for nonlinear optical properties, in photovoltaic devices, and as chemical sensors.

Photophysical properties of Au-CdTe hybrid nanostructures of varying sizes and shapes.

We design well-defined metal-semiconductor nanostructures using thiol-functionalized CdTe quantum dots (QDs)/quantum rods (QRs) with bovine serum albumin (BSA) protein-conjugated Au nanoparticles (NPs)/nanorods (NRs) in aqueous solution. The main focus of this article is to address the impacts of size and shape on the photophysical properties, including radiative and nonradiative decay processes and energy transfers, of Au-CdTe hybrid nanostructures. The red shifting of the plasmonic band and the strong photoluminescence (PL) quenching reveal a strong interaction between plasmons and excitons in these Au-CdTe hybrid nanostructures. The PL quenching of CdTe QDs varies from 40 to 86 % by changing the size and shape of the Au NPs. The radiative as well as the nonradiative decay rates of the CdTe QDs/QRs are found to be affected in the presence of both Au NPs and NRs. A significant change in the nonradiative decay rate from 4.72×10(6) to 3.92×10(10) s(-1) is obtained for Au NR-conjugated CdTe QDs. It is seen that the sizes and shapes of the Au NPs have a pronounced effect on the distance-dependent energy transfer. Such metal-semiconductor hybrid nanostructures should have great potentials for nonlinear optical properties, photovoltaic devices, and chemical sensors.

DNA Origami Directed Au Nanostar Dimers for Single-Molecule Surface-Enhanced Raman Scattering

We demonstrate the synthesis of Au nanostar dimers with tunable interparticle gap and controlled stoichiometry assembled on DNA origami. Au nanostars with uniform and sharp tips were immobilized on rectangular DNA origami dimerized structures to create nanoantennas containing monomeric and dimeric Au nanostars. Single Texas red (TR) dye was specifically attached in the junction of the dimerized origami to act as a Raman reporter molecule. The SERS enhancement factors of single TR dye molecules located in the conjunction region in dimer structures having interparticle gaps of 7 and 13 nm are 2 × 1010 and 8 × 109, respectively, which are strong enough for single analyte detection. The highly enhanced electromagnetic field generated by the plasmon coupling between sharp tips and cores of two Au nanostars in the wide conjunction region allows the accommodation and specific detection of large biomolecules. Such DNA-directed assembled nanoantennas with controlled interparticle separation distance and stoichiometry, and well-defined geometry, can be used as excellent substrates in single-molecule SERS spectroscopy and will have potential applications as a reproducible platform in single-molecule sensing.

Non-radiative relaxation and rectification behavior of metal/semiconductor tetrapod heterostructures

The metal-semiconductor hetero-structures have recently emerged as functional materials for their potential applications in the areas of photonic, optoelectronic, and other fields. Here, we discuss the structural characterization of Au/CdSe tetrapod hetero-structures by using high-resolution transmission electron microscope, high angle annular dark field-scanning transmission electron microscopic, and X-ray diffraction. The blue shifting of the plasmonic band and red shifting of the excitonic band suggest a strong surface plasmon-exciton interaction between Au and CdSe in Au/CdSe tetrapod heterostructure. A significant photoluminescence quenching (83.4%) of CdSe nanorod (NR) is observed in the presence of Au nanoparticle in Au/CdSe tetrapod heterostructure. The radiative and nonradiative decay rates of CdSe nanorods are found to be modified in Au/CdSe tetrapod structures and the nonradiative rate changes from 1.91 × 107 s−1 to 9.33 × 109 s−1 for CdSe NR to Au/CdSe tetrapod structure, respectively. Current...