Mita Dasog

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.

Size vs Surface: Tuning the Photoluminescence of Freestanding Silicon Nanocrystals Across the Visible Spectrum via Surface Groups

The syntheses of colloidal silicon nanocrystals (Si-NCs) with dimensions in the 3-4 nm size regime as well as effective methodologies for their functionalization with alkyl, amine, phosphine, and acetal functional groups are reported. Through rational variation in the surface moieties we demonstrate that the photoluminescence of Si-NCs can be effectively tuned across the entire visible spectral region without changing particle size. The surface-state dependent emission exhibited short-lived excited-states and higher relative photoluminescence quantum yields compared to Si-NCs of equivalent size exhibiting emission originating from the band gap transition. The Si-NCs were exhaustively characterized using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transformed infrared spectroscopy (FTIR), and their optical properties were thoroughly investigated using fluorescence spectroscopy, excited-state lifetime measurements, photobleaching experiments, and solvatochromism studies.

Silicon Nanocrystals and Silicon-Polymer Hybrids: Synthesis, Surface Engineering, and Applications

Silicon nanocrystals (Si-NCs) are emerging as an attractive class of quantum dots owing to the natural abundance of silicon in the Earths crust, their low toxicity compared to many Group II-VI and III-V based quantum dots, compatibility with the existing semiconductor industry infrastructure, and their unique optoelectronic properties. Despite these favorable qualities, Si-NCs have not received the same attention as Group II-VI and III-V quantum dots, because of their lower emission quantum yields, difficulties associated with synthesizing monodisperse particles, and oxidative instability. Recent advancements indicate the surface chemistry of Si-NCs plays a key role in determining many of their properties. This Review summarizes new reports related to engineering Si-NC surfaces, synthesis of Si-NC/polymer hybrids, and their applications in sensing, diodes, catalysis, and batteries.

Water-soluble photoluminescent D-mannose and L-alanine functionalized silicon nanocrystals and their application to cancer cell imaging

Herein, we report the straightforward synthesis, photoluminescent properties, and cell imaging studies of d-mannose and l-alanine functionalized silicon nanocrystals (SiNCs). Tailoring nanocrystal surface functionalization is essential to interfacing SiNCs with their environment and rendering them stable - surface modification also offers the opportunity to target specific cell types for imaging. A simple and versatile surface modification procedure was developed to tether biomolecules onto the SiNC surfaces and render them water-soluble. The presented approach is precious metal-catalyst free, straightforward, and provides carbohydrate and amino acid functionalized SiNCs. The functionalized SiNCs have been investigated by fluorescence microscopy and our results indicate that they can be internalized by MCF-7 human breast cancer cells as shown in the cell imaging studies. The obtained SiNCs were characterized using FTIR, XPS, PL, and TEM.

Size-controlled solid state synthesis of luminescent silicon nanocrystals using Stöber silica particles

Size-controlled Stober silica particles were prepared using a sol–gel methodology. The Stober silica particles were subsequently reduced using magnesium powder at 500 °C to yield silicon nanocrystals (Si-NCs) that were further reacted with trioctylphosphine oxide (TOPO) to yield hydroxyl terminated, TOPO encapsulated Si-NCs that exhibit red luminescence.

From Si and C encapsulated SiO2 to SiC: exploring the influence of sol–gel polymer substitution on thermally induced nanocrystal formation

Silicon-based nanomaterials are of far reaching interest because they can be biologically benign and highly photoluminescent. However if society is to make use of these properties efficient and predictable methods for preparing these materials must be realized. Here we report the syntheses of a series of sol–gel derived copolymers (i.e., [(HSiO1.5)0.95(RSiO1.5)0.5]n (where R = C2H5, C4H9, C6H13, C8H17, C10H21)) that yield silicon-based nanomaterials whose chemical composition and optical properties are strongly influenced by the nature of the R substituent. Freestanding nanomaterials were obtained through chemical etching of the resulting oxide matrices and some of these materials exhibited photoluminescence centered in the near-UV/visible spectral region. Composites and the etched materials were characterized using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).

Solid-state synthesis of luminescent silicon nitride nanocrystals

Silicon nitride nanocrystals (NCs) have been prepared via in situ nitridation of magnesium followed by a metathesis reaction with sol-gel derived silica particles. Highly luminescent, freestanding β-Si(3)N(4) NCs with complex surface chemistry dominated by Si-H and N-H moieties were isolated upon etching with hydrofluoric acid.

Profiling Photoinduced Carrier Generation in Semiconductor Microwire Arrays via Photoelectrochemical Metal Deposition

Au was photoelectrochemically deposited onto cylindrical or tapered p-Si microwires on Si substrates to profile the photoinduced charge-carrier generation in individual wires in a photoactive semiconductor wire array. Similar experiments were repeated for otherwise identical Si microwires doped to be n-type. The metal plating profile was conformal for n-type wires, but for p-type wires was a function of distance from the substrate and was dependent on the illumination wavelength. Spatially resolved charge-carrier generation profiles were computed using full-wave electromagnetic simulations, and the localization of the deposition at the p-type wire surfaces observed experimentally correlated well with the regions of enhanced calculated carrier generation in the volumes of the microwires. This technique could potentially be extended to determine the spatially resolved carrier generation profiles in a variety of mesostructured, photoactive semiconductors.

Silicon 1s near edge X-ray absorption fine structure spectroscopy of functionalized silicon nanocrystals

Silicon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of silicon nanocrystals have been examined as a function of nanocrystal size (3-100 nm), varying surface functionalization (hydrogen or 1-pentyl termination), or embedded in oxide. The NEXAFS spectra are characterized as a function of nanocrystal size and surface functionalization. Clear spectroscopic evidence for long range order is observed silicon nanocrystals that are 5-8 nm in diameter or larger. Energy shifts in the silicon 1s NEXAFS spectra of covalently functionalized silicon nanocrystals with changing size are attributed to surface chemical shifts and not to quantum confinement effects.