Band-Gap Tunability in Partially Amorphous Silicon Nanoparticles Using Single-Dot Correlative Microscopy.

Silicon nanoparticles (Si-NPs) represent one of many types of nanomaterials, where the origin of emission is difficult to assess due to a complex interplay between the core and surface chemistry. Band-gap tunability in Si-NPs is predicted to span from the infrared to the ultraviolet spectral range, which is rarely observed in practice. In this work, we directly assess the size dependence of the optical band gap using a single-dot correlative microscopy tool, where the size of the individual NPs is measured using atomic force microscopy (AFM) and the optical band gap is evaluated from single-dot photoluminescence measured on the very same NPs. We analyze 2-8 nm alkyl-capped Si-NPs prepared by a sol-gel method, followed by annealing at 1300 °C. Surprisingly, we find that the optical band gap is given by the amorphous shell, as evidenced by the convergence of the optical band gap size dependence toward the amorphous Si band gap of ∼1.56 eV. We propose that the structural disorder might be the reason behind the often reported limited emission tunability from various Si-NPs in the literature. We believe that our message points toward a pressing need for development and broader use of such direct correlative single-dot microscopy methods to avoid possible misinterpretations that could arise from attempts to recover size-band gap relation from ensemble methods, as practiced nowadays.

Critical assessment of wet-chemical oxidation synthesis of silicon quantum dots.

Wet-chemical synthetic procedures are powerful strategies to afford fluorescent silicon quantum dots (Si QDs) in a versatile and scalable manner. However, development of Si QDs is still hampered by a lack of control over photoluminescence emission, in addition to synthesis and characterization complexities. The wet-chemical Si QD synthesis by oxidation of magnesium silicide (Mg2Si) with bromine (Br2) was revisited and a control reaction was carried out where the silicon source was omitted. Both reaction conditions resulted in substantial quantities of fluorescent material. Moreover, a comparative analysis of their optical properties (UV-vis/fluorescence) revealed no apparent differences. Other characterization techniques also confirmed the resemblance of the two materials as 1H NMR, FTIR and XPS spectra were nearly identical for both samples. Elemental analysis revealed the presence of only 2 wt% silicon in the Si QD sample. No evidence was found for the formation of significant amounts of Si QDs via this wet-chemical procedure.

Photophysical properties of ball milled silicon nanostructures.

Luminescent silicon nanocrystals (SiNCs) have attracted scientific interest for their potential use in LEDs, displays, lasers, photovoltaic spectral-shifting filters and for biomedical applications. A lot of efforts have been made to improve the radiative emission rate in SiNCs, mostly using quantum confinement, strain and ligands. Existing methods, however, are not easily upscalable, as they do not provide the high material yield required for industrial applications. Besides, the photoluminescence (PL) efficiency of SiNCs emitting in the visible spectral range also remains very low. Hence, there is a need to develop a low-cost method for high material yield of brightly emitting SiNCs. Theoretically, strain can be used alongside quantum confinement to modify the radiative emission rates and band-gaps. In view of that, high-energy ball milling is a method that can be used to produce large quantities of highly strained SiNCs. In this technique, balls with high kinetic energy collide with the walls of a chamber and other balls, crushing the particles in between, followed by welding, fracture and re-welding phenomena, reducing the particle size and increasing strains in the samples. In this study, we have used high-energy ball milling in an inert gas atmosphere to synthesize SiNCs and study their photophysical properties. The induced accumulation of high strain, quantum confinement and possibly also impurities in the SiNCs resulted in visible light spectrum PL at room temperature. This method is low cost and easily up-scalable to industrial scale.

A New Lamellar Gold Thiolate Coordination Polymer, [Au(m-SPhCO2H)]n, for the Formation of Luminescent Polymer Composites.

The photoluminescence of gold thiolate clusters brings about many potential applications, but its origin is still elusive because of its complexity. A strategy in understanding the structure-properties relationship is to study closely related neutral gold thiolate coordination polymers (CPs). Here, a new CP is reported, [Au(m-SPhCO2H)]n. Its structure is lamellar with an inorganic layer made of Au-S-Au-S helical chains, similar to the [Au(p-SPhCO2H)]n analog. An in-depth study of its photophysical properties revealed that it is a bright yellow phosphorescent emitter with a band centered at 615 nm and a quantum yield (QY) of 19% at room temperature and in a solid state. More importantly, a comparison to the para-analog, which has a weak emission, displayed a strong effect of the position of the electron withdrawing group (EWG) on the luminescent properties. In addition, [Au(m-SPhCO2H)]n CPs were mixed with organic polymers to generate transparent and flexible luminescent thin films. The ability to tune the emission position with the appropriate contents makes these nontoxic polymer composites promising materials for lighting devices.

Hyperspectral sensing for turbid water quality monitoring in freshwater rivers: Empirical relationship between reflectance and turbidity and total solids.

Total suspended solid (TSS) is an important water quality parameter. This study was conducted to test the feasibility of the band combination of hyperspectral sensing for inland turbid water monitoring in Taiwan. The field spectral reflectance in the Wu river basin of Taiwan was measured with a spectroradiometer; the water samples were collected from the different sites of the Wu river basin and some water quality parameters were analyzed on the sites (in situ) as well as brought to the laboratory for further analysis. To obtain the data set for this study, 160 in situ sample observations were carried out during campaigns from August to December, 2005. The water quality results were correlated with the reflectivity to determine the spectral characteristics and their relationship with turbidity and TSS. Furthermore, multiple-regression (MR) and artificial neural network (ANN) were used to model the transformation function between TSS concentration and turbidity levels of stream water, and the radiance measured by the spectroradiometer. The value of the turbidity and TSS correlation coefficient was 0.766, which implies that turbidity is significantly related to TSS in the Wu river basin. The results indicated that TSS and turbidity are positively correlated in a significant way across the entire spectrum, when TSS concentration and turbidity levels were under 800 mg·L(-1) and 600 NTU, respectively. Optimal wavelengths for the measurements of TSS and turbidity are found in the 700 and 900 nm range, respectively. Based on the results, better accuracy was obtained only when the ranges of turbidity and TSS concentration were less than 800 mg·L(-1) and less than 600 NTU, respectively and used rather than using whole dataset (R(2) = 0.93 versus 0.88 for turbidity and R(2) = 0.83 versus 0.58 for TSS). On the other hand, the ANN approach can improve the TSS retrieval using MR. The accuracy of TSS estimation applying ANN (R(2) = 0.66) was better than with the MR approach (R(2) = 0.58), as expected due to the nonlinear nature of the transformation model.