Quantum confinement effects in silicon nanowires (SiNWs) are expected when their diameter is less than the size of the free exciton (with a Bohr radius ∼5 nm) in bulk silicon. However, their synthesis represents a considerable technological challenge. The vapor–liquid–solid (VLS) mechanism, mediated by metallic nanoclusters brought to the eutectic liquid state, is most widely used for its simplicity and control on the SiNWs size, shape, orientation, density, and surface smoothness. VLS growth is often performed within high-vacuum physical vapor deposition systems, where the eutectic composition and the pressure conditions define the minimum diameter of the final nanowire usually around 100 nm. In this article, we present and discuss the SiNWs’ growth by the VLS method in a plasma-based chemical vapor deposition system, working in the mTorr pressure range. The purpose is to demonstrate that it is possible to obtain nanostructures with sizes well beyond the observed limit by modulating the deposition parameters, like chamber pressure and plasma power, to find the proper thermodynamic conditions for nucleation. The formation of SiNWs with sub-5 nm diameter is demonstrated.

Semiconductor doping through solution-based self-assembling provides a simple, scalable, and cost-effective alternative to standard methods and additionally allows conformality on structured surfaces. Among the several solution-based deposition techniques, dip coating is the most promising. It consists in immersing the target to be doped inside a solution containing the dopant precursor. During this process, the molecule bonds to the target surface with a self-limiting process ruled by its steric properties. Successive annealing leads to layer decomposition and diffusion of dopant atoms inside the substrate. Most of the work on molecular doping lacks information on the molecule/Si interface chemical properties, on the mechanisms of the molecule evolution during the coating, and of its decomposition after the diffusion step. Moreover, it has so far been devoted to the molecules design to tune the final dopant dose and distribution. Here, the main results on the molecular doping are reviewed, and new findings on the interface characteristics, also in terms of monoand multilayers formation are presented. A systematic study, carried out by fixing the dopant precursor and varying the coating conditions, is also reported, demonstrating that the important doping features can be controlled precisely and that uniformity can be achieved at nanometer level.

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Silicon nanowires inspire since decades a great interest for their fundamental scientific importance and their potential in new technologies. When decorated with organic molecules they form hybrid composites with applications in various fields, from sensors to life science. Specifically the diethyl 1-propylphosphonate/Si combination is considered as a promising alternative to the conventional semiconductor n-type doping methods, thanks to its solution-based processing, which is damage-free and intrinsically conformal. For these characteristics, it is a valid doping process for patterned materials and nanostructures such as the nanowires. Our joined experimental and theoretical study provides insights at atomistic level on the molecular activation, grafting and self-assembling mechanisms during the deposition process. For the first time to the best of our knowledge, by using scanning transmission electron microscopy the direct visualization of the single molecules arranged over the Si nanowire surface is reported. The results demonstrate that the molecules undergo to a sequential decomposition and self-assembling mechanism, finally forming a chemical bond with the silicon atoms. The ability to prepare well-defined molecule decorated Si nanowires opens up new opportunities for fundamental studies and nanodevice applications in diverse fields like physics, chemistry, engineering and life sciences.

Molecular doping is a method to dope semiconductors based on the use of liquid solutions as precursors of the dopant. The molecules are deposited on the material, forming a self-ordered monolayer that conforms to the surfaces, whether they are planar or structured. So far, molecular doping has been used with precursors of organic molecules, which also release the carbon in the semiconductor. The carbon atoms, acting as traps for charge carriers, deteriorate the doping efficiency. For rapid and extensive industrial exploitation, the need for a method that removes carbon has therefore been raised. In this paper, we use phosphoric acid as a precursor of the dopant. It does not contain carbon and has a smaller steric footprint than the molecules used in the literature, thus allowing a much higher predetermined surface density. We demonstrate doses of electrical carriers as high as 3 × 1015 #/cm2, with peaks of 1 × 1020 #/cm3, and high repeatability of the process, indicating an outstanding yield compared to traditional MD methods.

Thanks to the silicon abundance, stability, non-toxicity and well known electronic properties, Si based solar cells have represented the leading actors in the photovoltaic market and future projections confirm this predominance. However, half of the module cost is due to the material consumption and processing. In order to decrease the costs, a cut in the Si consumption must be operated, with consequent decrement in the optical absorption, generated current and device efficiency. To keep the performance level, a proper Si surface design with the objective to trap the light, has been developed. One of the most popular approaches is to use silicon nanowires embedded in the solar cell emitter where they play the role of optically and electrically active layer, thanks to their excellent optical absorption properties. However, also another material has been the terminus of the light-trapping materials, the silicon nanoholes. Their mechanical robustness is superior, making their integration inside the cell easier and cost-effective. The review will bring about all of the most common methods to fabricate these two types of nanostructures when used for solar cells applications, their optical properties and some critical aspects related to their high surface to volume ratio which modify the recombination processes.

The molecular doping (MD) process consists of depositing a molecular precursor on a silicon substrate, covering the precursor with a cap layer and annealing the sample to decompose the precursor and diffuse dopant atoms within Si. In the literature, preliminary results have shown that dopant diffusion inside a substrate correlates with the presence or absence of the cap layer. The purpose of this work is to study how the cap coating changes the doping process and efficiency. The authors investigate and compare the electrical properties of silicon samples after MD doping with three different cap layers and without a cap layer. The authors examined a 500-nm-thick layer of SiO 2 deposited by spin-on-glass (SOG), a 500-nm-thick layer of SiO 2 deposited in a chemical vapor deposition (CVD) chamber at room temperature and a 100-nm-thick layer of oxidized silicon placed over and in contact with the samples to be doped. Spreading resistance profiling (SRP) measurements are then performed on these samples to monitor important doping features, such as carrier dose, carrier concentration, sheet resistance and junction depth, obtained with different capping conditions.