Ensemble Effects in the Temperature-Dependent Photoluminescence of Silicon Nanocrystals.

In this work the temperature-dependent photoluminescence of alkyl-capped silicon nanocrystals with mean diameters of between 3 and 9 nm has been investigated. The nanocrystals were characterized extensively by FTIR, TEM, powder XRD, and X-ray photoelectron spectroscopy prior to low-temperature and time-resolved photoluminescence spectroscopy experiments. The photoluminescence (PL) properties were evaluated in the temperature range of 41-300 K. We found that the well-known temperature-dependent blueshift of the PL maximum decreases with increasing nanocrystal diameter and eventually becomes a redshift for nanocrystal diameters larger than 6 nm. This implies that the observed shifts cannot be explained solely by band-gap widening, as is commonly assumed. We propose that the luminescence of drop-cast silicon nanocrystals is affected by particle ensemble effects, which can explain the otherwise surprising temperature dependence of the luminescence peak.

Observation of long-range dipole-dipole interactions in hyperbolic metamaterials.

Dipole-dipole interactions (V dd) between closely spaced atoms and molecules are related to real photon and virtual photon exchange between them and decrease in the near field connected with the characteristic Coulombic dipole field law. The control and modification of this marked scaling with distance have become a long-standing theme in quantum engineering since dipole-dipole interactions govern Van der Waals forces, collective Lamb shifts, atom blockade effects, and Förster resonance energy transfer. We show that metamaterials can fundamentally modify these interactions despite large physical separation between interacting quantum emitters. We demonstrate a two orders of magnitude increase in the near-field resonant dipole-dipole interactions at intermediate field distances (10 times the near field) and observe the distance scaling law consistent with a super-Coulombic interaction theory curtailed only by absorption and finite size effects of the metamaterial constituents. We develop a first-principles numerical approach of many-body dipole-dipole interactions in metamaterials to confirm our theoretical predictions and experimental observations. In marked distinction to existing approaches of engineering radiative interactions, our work paves the way for controlling long-range dipole-dipole interactions using hyperbolic metamaterials and natural hyperbolic two-dimensional materials.

The influence of conjugated alkynyl(aryl) surface groups on the optical properties of silicon nanocrystals: photoluminescence through in-gap states.

Developing new methods, other than size and shape, for controlling the optoelectronic properties of semiconductor nanocrystals is a highly desired target. Here we demonstrate that the photoluminescence (PL) of silicon nanocrystals (SiNCs) can be tuned in the range 685-800 nm solely via surface functionalization with alkynyl(aryl) (phenylacetylene, 2-ethynylnaphthalene, 2-ethynyl-5-hexylthiophene) surface groups. Scanning tunneling microscopy/spectroscopy on single nanocrystals revealed the formation of new in-gap states adjacent to the conduction band edge of the functionalized SiNCs. PL red-shifts were attributed to emission through these in-gap states, which reduce the effective band gap for the electron-hole recombination process. The observed in-gap states can be associated with new interface states formed via (-Si-C≡C-) bonds in combination with conjugated molecules as indicated by ab initio calculations. In contrast to alkynyl(aryl)s, the formation of in-gap states and shifts in PL maximum of the SiNCs were not observed with aryl (phenyl, naphthalene, 2-hexylthiophene) and alkynyl (1-dodecyne) surface groups. These outcomes show that surface functionalization with alkynyl(aryl) molecules is a valuable tool to control the electronic structure and optical properties of SiNCs via tuneable interface states, which may enhance the performance of SiNCs in semiconductor devices.

Engaging dual donor sites within an N-heterocyclic olefin phosphine ligand.

By investigating the coordination chemistry of a neutral N-heterocyclic olefin phosphine ligand, a new digold(i) chloride complex was discovered, demonstrating that mixed element (P/C) donor sites can be accessed at the same time. However attempts to extend this strategy for the preparation of heterobimetallic complexes featuring copper(i) and gold(i) centers with this mixed donor ligand were unsuccessful. The related monometallic copper(i) and gold(i) iodide complexes were discovered to be emissive in the solid state.

Lasing of whispering gallery modes in optofluidic microcapillaries.

This paper demonstrates lasing of the whispering gallery modes in polymer coated optofluidic capillaries and their application to refractive index sensing. The laser gain medium used here is fluorescent Nile Red dye, which is embedded inside the high refractive index polymer coating. We investigate the refractometric sensing properties of these devices for different coating thicknesses, revealing that the high Q factors required to achieve low lasing thresholds can only be realized for relatively thick polymer coatings (in this case ≥ 800 nm). Lasing capillaries therefore tend to have a lower refractive index sensitivity, compared to non-lasing capillaries which can have a thinner polymer coating, due to the stronger WGM confinement within the polymer layer. However we find that the large improvement in signal-to-noise ratio realized for lasing capillaries more than compensates for the decreased sensitivity and results in an order-of-magnitude improvement in the detection limit for refractive index sensing.

Photoluminescence through in-gap states in phenylacetylene functionalized silicon nanocrystals.

Optoelectronic properties of Si nanocrystals (SiNCs) were studied by combining scanning tunneling spectroscopy (STS) and optical measurements. The photoluminescence (PL) of phenylacetylene functionalized SiNCs red shifts relative to hexyl- and phenyl-capped counterparts, whereas the absorption spectra and the band gaps extracted from STS are similar for all surface groups. However, an in-gap state near the conduction band edge was detected by STS only for the phenylacetylene terminated SiNCs, which can account for the PL shift via relaxation across this state.

Detection of nitroaromatics in the solid, solution, and vapor phases using silicon quantum dot sensors.

Silicon quantum dots (Si-QDs) represent a well-known QD fluorophore that can emit throughout the visible spectrum depending on the interface structure and surface functional group. Detection of nitroaromatic compounds by monitoring the luminescence response of the sensor material (typically fluorescent polymers) currently forms the basis of new explosives sensing technologies. Freestanding silicon QDs may represent a benign alternative with a high degree of chemical and physical versatility. Here, we investigate dodecyl and amine-terminated Si-QD luminescence response to the presence of nitrobenzene and dinitrotoluene (DNT) in various solid, solution, and vapor forms. For dinitrotoluene vapor the 3σ detection limit was 6 ppb for monomer-terminated QDs. For nitroaromatics dissolved in toluene the detection limit was on the order of 400 nM, corresponding to ∼100 pg of material distributed over ∼1 cm(2) on the sensor surface. Solid traces of nitroaromatics were also easily detectable via a simple 'touch test'. The samples showed minimal interference effects from common contaminants such as water, ethanol, and acetonitrile. The sensor can be as simple and inexpensive as a small circle of filter paper dipped into a QD solution, with a single vial of QDs able to make hundreds of these sensors. Additionally, a trial fiber-optic sensor device was tested by applying the QDs to one end of a 2 × 2 fiber coupler and exposing them to controlled DNT vapor. Finally, the quenching mechanism was explored via luminescence dynamics measurements and is different for blue (amine) and red (dodecyl) fluorescent silicon QDs.

Radical Initiated Hydrosilylation on Silicon Nanocrystal Surfaces: An Evaluation of Functional Group Tolerance and Mechanistic Study.

Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

Synthesis and operation of fluorescent-core microcavities for refractometric sensing.

This paper discusses fluorescent core microcavity-based sensors that can operate in a microfluidic analysis setup. These structures are based on the formation of a fluorescent quantum-dot (QD) coating on the channel surface of a conventional microcapillary. Silicon QDs are especially attractive for this application, owing in part to their negligible toxicity compared to the II-VI and II-VI compound QDs, which are legislatively controlled substances in many countries. While the ensemble emission spectrum is broad and featureless, an Si-QD film on the channel wall of a capillary features a set of sharp, narrow peaks in the fluorescence spectrum, corresponding to the electromagnetic resonances for light trapped within the film. The peak wavelength of these resonances is sensitive to the external medium, thus permitting the device to function as a refractometric sensor in which the QDs never come into physical contact with the analyte. The experimental methods associated with the fabrication of the fluorescent-core microcapillaries are discussed in detail, as well as the analysis methods. Finally, a comparison is made between these structures and the more widely investigated liquid-core optical ring resonators, in terms of microfluidic sensing capabilities.

A convenient method for electron tomography sample preparation using a focused ion beam.

Here we report a new sample preparation method for three-dimensional electron tomography. The method uses the standard film deposition and focused ion beam (FIB) methods to significantly reduce the problems arising from the projected sample thickness at high tilt angles. The method can be used to prepare tomography samples that can be imaged up to a ±75° tilt range which is sufficient for many practical applications. The method can minimize the problem of Ga⁺ contamination, as compared to the case of FIB preparation of rod-shaped samples, and provides extended thin regions for standard 2D projection analyses.

Heteroepitaxial growth of gold nanostructures on silicon by galvanic displacement.

This work focuses on the synthesis and interfacial characterization of gold nanostructures on silicon surfaces, including Si(111), Si(100), and Si nanowires. The synthetic approach uses galvanic displacement, a type of electroless deposition that takes place in an efficient manner under aqueous, room-temperature conditions. The case of gold-on-silicon has been widely studied and used for several applications and yet, a number of important, fundamental questions remain as to the nature of the interface. Some studies are suggestive of heteroepitaxial growth of gold on the silicon surface, whereas others point to the existence of a silicon-gold intermetallic sandwiched between the metallic gold and the underlying silicon substrate. Through detailed high resolution transmission electron microscopy (TEM), combined with selected area electron diffraction (SAED) and nanobeam diffraction (NBD), heteroepitaxial gold that is grown by galvanic displacement is confirmed on both Si(100) and Si(111), as well as silicon nanowires. The coincident site lattice (CSL) of gold-on-silicon results in a very small 0.2% lattice mismatch due to the coincidence of four gold lattices to three of silicon. The presence of gold-silicon intermetallics is suggested by the appearance of additional spots in the electron diffraction data. The gold-silicon interfaces appear heterogeneous with distinct areas of heteroepitaxial gold on silicon, and others, less well-defined, where intermetallics may reside. The high resolution cross-sectional TEM images reveal a roughened silicon interface under these aqueous galvanic displacement conditions, which most likely promotes nucleation of metallic gold islands that merge over time: a Volmer-Weber growth mechanism in the initial stages.

Preparation of alkyl-surface functionalized germanium quantum dots via thermally initiated hydrogermylation.

A new, thermally initiated hydrogermylation-based method for the synthesis and surface functionalization of air- and moisture-stable germanium quantum dots is reported.