Removal of Ag remanence and improvement in structural attributes of silicon nanowires array via sintering

Metal-assisted chemical etching (MACE) is popular due to the large-area fabrication of silicon nanowires (SiNWs) exhibiting a high aspect ratio at a low cost. The remanence of metal, i.e., silver nanoparticles (AgNPs) used in the MACE, deteriorates the device (especially solar cell) performance by acting as a defect center. The superhydrophobic behavior of nanowires (NWs) array prohibits any liquid-based solution (i.e., thorough cleaning with HNO3 solution) from removing the AgNPs. Thermal treatment of NWs is an alternative approach to reduce the Ag remanence. Sintering temperature variation is chosen between the melting temperature of bulk-Ag (962 °C) and bulk-Si (1412 °C) to reduce the Ag particles and improve the crystallinity of the NWs. The melting point of NWs decreases due to surface melting that restricts the sintering temperature to 1200 °C. The minimum sintering temperature is set to 1000 °C to eradicate the Ag remanence. The SEM–EDS analysis is carried out to quantify the reduction in Ag remanence in the sintered NWs array. The XRD analysis is performed to study the oxides (SiO and Ag2O) formed in the NWs array due to the trace oxygen level in the furnace. The TG-DSC characterization is carried out to know the critical sintering temperature at which remanence of AgNPs removes without forming any oxides. The Raman analysis is studied to determine the crystallinity, strain, and size of Si nanocrystals (SiNCs) formed on the NWs surface due to sidewalls etching. An optimized polynomial equation is derived to find the SiNCs size for various sintering temperatures.

Effect of the Graded Silicon Content in SRN/SRO Multilayer Structures on the Si Nanocrystals and Si Nanopyramids Formation and Their Photoluminescence Response

Two multilayer (ML) structures, composed of five layers of silicon-rich oxide (SRO) with different Si contents and a sixth layer of silicon-rich nitride (SRN), were deposited by low pressure chemical vapor deposition. These SRN/SRO MLs were thermally annealed at 1100 °C for 180 min in ambient N2 to induce the formation of Si nanostructures. For the first ML structure (MLA), the excess Si in each SRO layer was about 10.7 ± 0.6, 9.1 ± 0.4, 8.0 ± 0.2, 9.1 ± 0.3 and 9.7 ± 0.4 at.%, respectively. For the second ML structure (MLB), the excess Si was about 8.3 ± 0.2, 10.8 ± 0.4, 13.6 ± 1.2, 9.8 ± 0.4 and 8.7 ± 0.1 at.%, respectively. Si nanopyramids (Si-NPs) were formed in the SRO/Si substrate interface when the SRO layer with the highest excess silicon (10.7 at.%) was deposited next to the MLA substrate. The height, base and density of the Si-NPs was about 2–8 nm, 8–26 nm and ~6 × 1011 cm−2, respectively. In addition, Si nanocrystals (Si-ncs) with a mean size of between 3.95 ± 0.20 nm and 2.86 ± 0.81 nm were observed for the subsequent SRO layers. Meanwhile, Si-NPs were not observed when the excess Si in the SRO film next to the Si-substrate decreased to 8.3 ± 0.2 at.% (MLB), indicating that there existed a specific amount of excess Si for their formation. Si-ncs with mean size of 2.87 ± 0.73 nm and 3.72 ± 1.03 nm were observed for MLB, depending on the amount of excess Si in the SRO film. An enhanced photoluminescence (PL) emission (eight-fold more) was observed in MLA as compared to MLB due to the presence of the Si-NPs. Therefore, the influence of graded silicon content in SRN/SRO multilayer structures on the formation of Si-NPs and Si-ncs, and their relation to the PL emission, was analyzed.

Morphology and photoluminescence properties of silicon nanoparticles deposited in helium-nitrogen mixtures maintained at low residual pressures

We elaborated a technique of pulsed laser ablation in gas mixtures (He-N2), maintained under residual pressures of 0.5–5 Torr to deposit silicon (Si)-based nanostructured films on a substrate. We show that the deposited films can exhibit strong photoluminescence (PL) emission with the position of peaks depending on the pressure of ambient gas and the ratio of gases in the mixture. Nanostructured films prepared in pure He gas exhibited a strong band in the infrared range (around 760 nm) and a weak band in the green range (550 nm), which were attributed to quantum-confined excitonic states in small Si nanocrystals and radiative transitions via the localized electronic states in silicon suboxide coating, respectively. In contrast, nanostructured films prepared in He-N2 mixtures exhibited more intense “green-yellow” PL band centered at 580 nm, which was attributed to a radiative recombination in amorphous oxynitride (a-SiNxOy) coating of Si nanocrystals. We also present a detailed analysis of morphology of nanostructures Si-based films prepared by laser ablation. Finally, we show that the nanocrystals can be removed from the substrate and milled by ultrasound to form aqueous solutions of colloidal Si nanopartiles. The fabricated Si-based nanocrystals present a promising object for theranostics, combining imaging functionality based on PL emission and a series of therapy functionalities (photo and radiofrequency hyperthermia, photodynamic therapy).

Derivation of Luminescent Mesoporous Silicon Nanocrystals from Biomass Rice Husks by Facile Magnesiothermic Reduction

High-quality silicon (Si) nanocrystals that simultaneously had superior mesoporous and luminescent characteristics were derived from sticky, red, and brown rice husks via the facile and cost-effective magnesiothermic reduction method. The Si nanocrystals were confirmed to comprise an aggregated morphology with spherical nanocrystals (e.g., average sizes of 15–50 nm). Due to the surface functional groups formed at the nanocrystalline Si surfaces, the Si nanocrystals clearly exhibited multiple luminescence peaks in visible-wavelength regions (i.e., blue, green, and yellow light). Among the synthesized Si nanocrystals, additionally, the brown rice husk (BRH)-derived Si nanocrystals showed to have a strong UV absorption and a high porosity (i.e., large specific surface area: 265.6 m2/g, small average pore diameter: 1.91 nm, and large total pore volume: 0.5389 cm3/g). These are indicative of the excellent optical and textural characteristics of the BRH-derived Si nanocrystals, compared to previously reported biomass-derived Si nanocrystals. The results suggest that the biomass BRH-derived Si nanocrystals hold great potential as an active source material for optoelectronic devices as well as a highly efficient catalyst or photocatalyst for energy conversion devices.