Shape and Phase-Controlled One-Pot Synthesis of Air Stable Cationic AgCdS Nanocrystals, Optoelectronic and Electrochemical Hydrogen Evolution Studies.

CdS-based materials are extensively studied for photocatalytic water splitting. By incorporating Ag+ into CdS nanomaterials, the catalyst's charge carrier dynamic can be tuned for photo-electrochemical devices. However, photo-corrosion and air-stability of the heterostructures limit the photocatalytic device's performance. Here, a one-pot, single molecular source synthesis of the air-stable AgCdS ternary semiconductor alloy nanostructures by heat-up method is reported. Monoclinic and hexagonal phases of the alloy are tuned by judicious choice of dodecane thiol (DDT), octadecyl amine (ODA), and oleyl amine (OLA) as capping agents. Transmission electron microscope (TEM) and powder X-ray diffraction characterization of the AgCdS alloy confirm the monoclinic and hexagonal phase (wurtzite) formation. The high-resolution TEM studies confirm the formation of AgCdS@DDT alloy nanorods and their shape transformation into nano-triangles. The nanoparticle coalescence is observed for ODA-capped alloys in the wurtzite phase. Moreover, OLA directs mixed crystal phases and anisotropic growth of alloy. Optical processes in AgCdS@DDT nano-triangles show mono-exponential decay (3.97 ± 0.01 ns). The monoclinic phase of the AgCdS@DDT nanorods exhibits higher electrochemical hydrogen evolution activity in neutral media as compared to the AgCdS@ODA/OLA alloy nanocrystals. DDT and OLA-capped alloys display current densities of 14.1 and 14.7 mA cm-2 , respectively, at 0.8 V (vs RHE).

Nanoantenna enhanced terahertz interaction of biomolecules.

Terahertz time-domain spectroscopy (THz-TDS) is a non-invasive, non-contact and label-free technique for biological and chemical sensing as THz-spectra are less energetic and lie in the characteristic vibration frequency regime of proteins and DNA molecules. However, THz-TDS is less sensitive for the detection of micro-organisms of size equal to or less than λ/100 (where, λ is the wavelength of the incident THz wave), and molecules in extremely low concentration solutions (like, a few femtomolar). After successful high-throughput fabrication of nanostructures, nanoantennas were found to be indispensable in enhancing the sensitivity of conventional THz-TDS. These nanostructures lead to strong THz field enhancement when in resonance with the absorption spectrum of absorptive molecules, causing significant changes in the magnitude of the transmission spectrum, therefore, enhancing the sensitivity and allowing the detection of molecules and biomaterials in extremely low concentration solutions. Herein, we review the recent developments in ultra-sensitive and selective nanogap biosensors. We have also provided an in-depth review of various high-throughput nanofabrication techniques. We also discussed the physics behind the field enhancements in the sub-skin depth as well as sub-nanometer sized nanogaps. We introduce finite-difference time-domain (FDTD) and molecular dynamics (MD) simulation tools to study THz biomolecular interactions. Finally, we provide a comprehensive account of nanoantenna enhanced sensing of viruses (like, H1N1) and biomolecules such as artificial sweeteners which are addictive and carcinogenic.

Deterministic coupling of quantum emitters in WSe2 monolayers to plasmonic nanocavities.

We discuss coupling of site-selectively induced quantum emitters in exfoliated monolayers of WSe2 to plasmonic nanostructures. Gold nanorods of 20 nm-240 nm size, which are arranged in pitches of a few micrometers on a dielectric surface, act as seeds for the formation of quantum emitters in the atomically thin materials. We observe characteristic narrow-band emission signals from the monolayers, which correspond well with the positions of the metallic nanopillars with and without thin dielectric coating. Single photon emission from the emitters is confirmed by autocorrelation measurements, yielding g2(τ = 0) values as low as 0.17. Moreover, we observe a strong co-polarization of our single photon emitters with the frequency matched plasmonic resonances, as a consequence of light-matter coupling. Our work represents a significant step towards the scalable implementation of coupled quantum emitter-resonator systems for highly integrated quantum photonic and plasmonic applications.

Quantum dots-nanogap metamaterials fabrication by self-assembly lithography and photoluminescence studies.

We present a new and versatile technique of self-assembly lithography to fabricate a large scale Cadmium selenide quantum dots-silver nanogap metamaterials. After optical and electron microscopic characterizations of the metamaterials, we performed spatially resolved photoluminescence transmission measurements. We obtained highly quenched photoluminescence spectra compared to those from bare quantum dots film. We then quantified the quenching in terms of an average photoluminescence enhancement factor. A finite difference time domain simulation was performed to understand the role of an electric field enhancement in the nanogap over this quenching. Finally, we interpreted the mechanism of the photoluminescence quenching and proposed fabrication method of new metamaterials using our technique.