To fully exploit van der Waals materials and their vertically stacked heterostructures, new mass-scalable production routes which are low cost but preserve the high electronic and optical quality of the single crystals are required. Here, we demonstrate an approach to realise a variety of functional heterostructures based on van der Waals nanocrystal films produced through the mechanical abrasion of bulk powders. We find significant performance enhancements in abraded heterostructures compared to those fabricated through inkjet printing of nanocrystal dispersions. To highlight the simplicity, applicability and scalability of the device fabrication, we demonstrate a multitude of different functional heterostructures such as resistors, capacitors and photovoltaics. We also demonstrate the creation of energy harvesting devices, such as large area catalytically active coatings for the hydrogen evolution reaction and enhanced triboelectric nanogenerator performance in multilayer films. The ease of device production makes this a promising technological route for up-scalable films and heterostructures.

High capacitance density three-dimensional (3D) metal-insulator-semiconductor (MIS) capacitors using Si nanowires (SiNWs) by metal-assisted chemical etching and atomic-layer-deposited alumina dielectric film were fabricated and electrically characterized. A chemical treatment was used to remove structural defects from the nanowire surface, in order to reduce the density of interface traps at the Al2O3/SiNW interface. SiNWs with two different lengths, namely, 1.3 μm and 2.4 μm, were studied. A four-fold capacitance density increase compared to a planar reference capacitor was achieved with the 1.3 μm SiNWs. In the case of the 2.4 μm SiNWs this increase was ×7, reaching a value of 4.1 μF/cm2. Capacitance-voltage (C-V) measurements revealed that, following a two-cycle chemical treatment, frequency dispersion at accumulation regime and flat-band voltage shift disappeared in the case of the 1.3 μm SiNWs, which is indicative of effective removal of structural defects at the SiNW surface. In the case of the 2.4 μm SiNWs, frequency dispersion at accumulation persisted even after the two-step chemical treatment. This is attributed to a porous Si layer at the SiNW tops, which is not effectively removed by the chemical treatment. The electrical losses of MIS capacitors in both cases of SiNW lengths were studied and will be discussed.

The structure and light-emitting properties of Si nanowires (SiNWs) fabricated by a single-step metal-assisted chemical etching (MACE) process on highly boron-doped Si were investigated after different chemical treatments. The Si nanowires that result from the etching of a highly doped p-type Si wafer by MACE are fully porous, and as a result, they show intense photoluminescence (PL) at room temperature, the characteristics of which depend on the surface passivation of the Si nanocrystals composing the nanowires. SiNWs with a hydrogen-terminated nanostructured surface resulting from a chemical treatment with a hydrofluoric acid (HF) solution show red PL, the maximum of which is blueshifted when the samples are further chemically oxidized in a piranha solution. This blueshift of PL is attributed to localized states at the Si/SiO2 interface at the shell of Si nanocrystals composing the porous SiNWs, which induce an important pinning of the electronic bandgap of the Si material and are involved in the recombination mechanism. After a sequence of HF/piranha/HF treatment, the SiNWs are almost fully dissolved in the chemical solution, which is indicative of their fully porous structure, verified also by transmission electron microscopy investigations. It was also found that a continuous porous Si layer is formed underneath the SiNWs during the MACE process, the thickness of which increases with the increase of etching time. This supports the idea that porous Si formation precedes nanowire formation. The origin of this effect is the increased etching rate at sites with high dopant concentration in the highly doped Si material.

Si nanowires (SiNWs) produced by metal-assisted chemical etching on n-type Si were investigated for their use as a light-trapping material in c-Si solar cells. The nanowires were fabricated before junction formation (on a lightly doped Si substrate) so that their core was bulk and nonporous. The above fabrication process was implemented in solar cell fabrication. The SiNW reflectivity was tested at different steps of solar cell processing and found to be lower than that of conventional random pyramids used in c-Si solar cells. Contact formation on the front side of the cell was investigated by considering metal deposition either directly on the nanowires or on bulk areas in between the nanowire areas. The superiority of this second case was demonstrated. Three different Si nanowire lengths were investigated, namely, 0.5, 1, and 1.5 μm, the case of 1 μm giving better results in terms of solar cell characteristics and external quantum efficiency. The electronic quality of the Si nanowire surface was investigated using the corresponding metal-oxide-semiconductor capacitors with atomic-layer-deposited alumina dielectric. Successful reduction of surface recombination centers at the large Si nanowire surface was achieved by reducing structural defects at their surface through a specific chemical treatment. Finally, using the determined optimized conditions for Si nanowire formation, chemical cleaning, and process implementation in solar cell fabrication, we demonstrated ∼45% increase in solar cell efficiency with 1 μm SiNWs compared to that from a flat reference cell processed under similar conditions. The above study was made on test solar cells without surface passivation.

High-density silicon nanowires (SiNWs) were fabricated on p-Si substrates by metal-assisted chemical etching (MACE). A chemical cleaning with HF/piranha/HF was used to remove structural defects from the nanowire surface which are at the origin of surface recombination states. Surface photovoltage (SPV) spectroscopy, capacitance− voltage (C−V), and conductance measurements were used to study the SiNW properties and assess the effectiveness of the cleaning process. For the as-grown samples, the analysis of the SPV amplitude and phase spectra demonstrated high density of positively charged surface recombination centers. These centers increase the surface band bending and decrease the minority carrier lifetime and diffusion length. Si nanostructures at the SiNW surface introduce slow traps, as evidenced by the frequency dispersion at accumulation of the C−V curves and the increase of the diffusion length with frequency. All these features are effectively reduced when the SiNWs are subjected to HF/piranha/HF chemical cleaning. Thus, a cheap and effective way is demonstrated to reduce the surface state density and improve the electronic quality of the surface of SiNWs.