Elayaraja Muthuswamy

Chemical Insight into the Origin of Red and Blue Photoluminescence Arising from Freestanding Silicon Nanocrystals

Silicon nanocrystals (Si NCs) are attractive functional materials. They are compatible with standard electronics and communications platforms and are biocompatible. Numerous methods have been developed to realize size-controlled Si NC synthesis. While these procedures produce Si NCs that appear identical, their optical responses can differ dramatically. Si NCs prepared using high-temperature methods routinely exhibit photoluminescence agreeing with the effective mass approximation (EMA), while those prepared via solution methods exhibit blue emission that is somewhat independent of particle size. Despite many proposals, a definitive explanation for this difference has been elusive for no less than a decade. This apparent dichotomy brings into question our understanding of Si NC properties and potentially limits the scope of their application. The present contribution takes a substantial step forward toward identifying the origin of the blue emission that is not expected based upon EMA predictions. It describes a detailed comparison of Si NCs obtained from three of the most widely cited procedures as well as the conversion of red-emitting Si NCs to blue emitters upon exposure to nitrogen-containing reagents. Analysis of the evidence is consistent with the hypothesis that the presence of trace nitrogen and oxygen even at the parts per million level in Si NCs gives rise to the blue emission.

Development of Iron-Doped Silicon Nanoparticles As Bimodal Imaging Agents

We demonstrate the synthesis of water-soluble allylamine-terminated Fe-doped Si (Si(xFe)) nanoparticles as bimodal agents for optical and magnetic imaging. The preparation involves the synthesis of a single-source iron-containing precursor, Na(4)Si(4) with x% Fe (x = 1, 5, 10), and its subsequent reaction with NH(4)Br to produce hydrogen-terminated Si(xFe) nanoparticles. The hydrogen-capped nanoparticles are further terminated with allylamine via thermal hydrosilylation. Transmission electron microscopy indicates that the average particle diameter is ∼3.0 ± 1.0 nm. The Si(5Fe) nanoparticles show strong photoluminescence quantum yield in water (∼10%) with significant T(2) contrast (r(2)/r(1) value of 4.31). Electron paramagnetic resonance and Mössbauer spectroscopies indicate that iron in the nanoparticles is in the +3 oxidation state. Analysis of cytotoxicity using the resazurin assay on HepG2 liver cells indicates that the particles have minimal toxicity.

Quantum dot Ge/TiO2 heterojunction photoconductor fabrication and performance

Spun cast TiO2-Ge quantum dot (QD) heterojunction type photodetectors have been fabricated and characterized, with interest paid to photocurrent enhancements related to device design. Performance as a function of absorber layer thickness, QD size, and back contact is investigated. We have achieved ultra-thin (∼200 nm) devices with photocurrents at 0.5 V of 10−4 A cm−2 while the thickest devices have photocurrents at 0.5 V of 10−2 A cm−2 with on-off ratios >100, which represents 5 orders of magnitude increase in photocurrents over previously fabricated Ge QD devices. At 0.5 V bias, the currents in our devices are competitive with thin-film Ge photovoltaics.

Sacrificial Silver Nanoparticles: Reducing GeI2 To Form Hollow Germanium Nanoparticles by Electroless Deposition

Herein we report the electroless deposition of Ge onto sacrificial Ag nanoparticle (NP) templates to form hollow Ge NPs. The formation of AgI is a necessary component for this reaction. Through a systematic study of surface passivating ligands, we determined that tri-n-octylphosphine is necessary to facilitate the formation of hollow Ge NPs by acting as a transport agent for GeI2 and the oxidized Ag(+) cation (i.e., AgI product). Annular dark-field (ADF) scanning transmission electron microscopy (STEM) imaging of incomplete reactions revealed Ag/Ge core/shell NPs; in contrast, completed reactions displayed hollow Ge NPs with pinholes which is consistent with the known method for dissolution of the nanotemplate. Characterization of the hollow Ge NPs was performed by transmission electron microscopy, ADF-STEM, energy-dispersive X-ray spectroscopy, UV-vis spectrophotometry, and Raman spectroscopy. The galvanic replacement reaction of Ag with GeI2 offers a versatile method for controlling the structure of Ge nanomaterials.