Microwave-assisted synthesis of II-VI semiconductor micro-and nanoparticles towards sensor applications.

摘要

Engineering particles at the nanoscale demands a high degree of control over process parameters during synthesis. For nanocrystal synthesis, solution-based techniques typically include application of external convective heat. This process often leads to slow heating and allows decomposition of reagents or products over time. Microwave-assisted heating provides faster, localized heating at the molecular level with near instantaneous control over reaction parameters. In this work, microwave-assisted heating has been applied for the synthesis of II-VI semiconductor nanocrystals namely, ZnO nanopods and CdX (X = Se, Te) quantum dots (QDs). Based on factors such as size, surface functionality and charge, optical properties of such nanomaterials can be tuned for application as sensors.;ZnO is a direct bandgap semiconductor (3.37 eV) with a large exciton binding energy (60 meV) leading to photoluminescence (PL) at room temperature. A microwave-assisted hydrothermal approach allows the use of sub-5 nm ZnO zero-dimensional nanoparticles as seeds for generation of multi-legged quasi one-dimensional nanopods via heterogeneous nucleation. ZnO nanopods, having individual leg diameters of 13-15 nm and growing along the [0001] direction, can be synthesized in as little as 20 minutes. ZnO nanopods exhibit a broad defect-related PL spanning the visible range with a peak at ~615 nm. Optical sensing based on changes in intensity of the defect PL in response to external environment (e.g., humidity) is demonstrated in this work.;Microwave-assisted synthesis was also used for organometallic synthesis of CdX(ZnS) (X = Se, Te) core(shell) QDs. Optical emission of these QDs can be altered based on their size and can be tailored to specific wavelengths. Further, QDs were incorporated in Enhanced Green-Fluorescent Protein – Ultrabithorax (EGFP-Ubx) fusion protein for the generation of macroscale composite protein fibers via hierarchal self-assembly. Variations in EGFP- Ubx˙QD composite fiber surface morphology and internal QD distribution were studied with respect to (i) time of QD addition (i.e., pre or post protein self-assembly) and (ii) QD surface charge—negatively charged QDs with dihydrolipoic acid functionalization and positively charged QDs with polyethyleneimine coating.;Elucidating design motifs and understanding factors that impact the protein-nanoparticle interaction enables manipulation of the structure and mechanical properties of composite materials.