P/n and n/p junctions with depths of 200 nm to several micrometers have been created in flat silicon substrates as well as on 3D microstructures by means of a variety of methods, including solid source dotation (SSD), low‐pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition, and plasma‐enhanced chemical vapor deposition. Radial junctions in Si micropillars are inspected by optical and scanning electron micro­scopies, using a CrO3‐based staining solution, which enables visualization of the junction depth. When applying identical‐doping parameters to flat substrates, ball grooving, followed by staining and optical microscopy, yields similar junction depth values as high‐resolution scanning electron microscopy imaging on stained cross‐sections and secondary ion mass spectrometry depth profilometry. For the investigated 3D microstructures, doping based on SSD and LPCVD give uniform and conformal junctions. Junctions made with SSD‐boron doping and CVD‐phosphorus doping could be accurately predicted with a model based on Fick's diffusion law. 3D‐microstructured silicon pillar arrays show an increased efficiency for sunlight capturing. The functionality of micropillar arrays with radial junctions is evidenced by improved short‐circuit current densities and photovoltaic efficiencies compared with flat surfaces, for both n‐ and p‐type wafers (average pillar arrays efficiencies of 9.4% and 11%, respectively, compared with 8.3% and 6.4% for the flat samples).

Silicon is one of the main components of commercial solar cells and is used in many other solar-light-harvesting devices. The overall efficiency of these devices can be increased by the use of structured surfaces that contain nanometer- to micrometer-sized pillars with radial p/n junctions. High densities of such structures greatly enhance the light-absorbing properties of the device, whereas the 3D p/n junction geometry shortens the diffusion length of minority carriers and diminishes recombination. Due to the vast silicon nano- and microfabrication toolbox that exists nowadays, many versatile methods for the preparation of such highly structured samples are available. Furthermore, the formation of p/n junctions on structured surfaces is possible by a variety of doping techniques, in large part transferred from microelectronic circuit technology. The right choice of doping method, to achieve good control of junction depth and doping level, can contribute to an improvement of the overall efficiency that can be obtained in devices for energy applications. A review of the state-of-the-art of the fabrication and doping of silicon micro and nanopillars is presented here, as well as of the analysis of the properties and geometry of thus-formed 3D-structured p/n junctions.

The effects of pillar height and junction depth on solar cell characteristics are investigated to provide design rules for arrays of such pillars in solar energy applications. Radially doped silicon pillar arrays are fabricated by deep reactive ion etching of silicon substrates followed by the introduction of dopant atoms by diffusion from a phosphorus oxide layer conformally deposited by low‐pressure chemical vapor deposition. Increasing the height of the pillars has led to doubling of the efficiency from 6% for flat substrates to 12% for 40 μm high pillars with a 900 nm junction depth because of an increase in the total junction area and lower optical reflection. For higher pillars, the current density and efficiency is decreased, which is attributed to the increasing presence of defect states at the surface introduced during the etching process. This effect can be counteracted by an Al2O3 passivation layer on the pillar surface. An optimum efficiency of 13% is found for a junction depth of 790 nm for 40 μm pillar height. At increased junction depths, the efficiency is decreased due to the ever thinner undoped core of the pillars, causing pillars with a large junction depth to become less efficient than flat silicon substrates.

In order to assess the contributions of anti‐reflective and passivation effects in microstructured silicon‐based solar light harvesting devices, thin layers of aluminum oxide (Al2O3), silicon dioxide (SiO2), silicon‐rich silicon nitride (SiNx), and indium tin oxide (ITO), with a thickness ranging from 45 to 155 nm, are deposited onto regularly packed arrays of silicon micropillars with radial p/n junctions. Atomic layer deposition of Al2O3 yields the best conformal coating over the micropillars. The fact that layers made by low‐pressure chemical vapor deposition (SiO2 and SiNx) are not conformally deposited on the sidewalls of the Si micropillars do not influence the photoelectrical efficiency. For ITO, a change in composition along the micropillar height is measured, which leads to poor performance. For Al2O3, deconvolution of the contributions of passivation and anti‐reflection to the overall efficiency gain exhibits the importance of passivation in micro/nano‐structured Si devices. Al2O3‐coated samples perform the best, for both n/p and p/n configured pillars, yielding (relative) increases of 116% and 37% in efficiency of coated versus non‐coated samples for p‐type and n‐type base micropillar arrays, respectively.

Silicon-based solar fuel devices require passivation for optimal performance yet at the same time need functionalization with (photo)catalysts for efficient solar fuel production. Here, we use molecular monolayers to enable electrical passivation and simultaneous functionalization of silicon-based solar cells. Organic monolayers were coupled to silicon surfaces by hydrosilylation in order to avoid an insulating silicon oxide layer at the surface. Monolayers of 1-tetradecyne were shown to passivate silicon micropillar-based solar cells with radial junctions, by which the efficiency increased from 8.7% to 9.9% for n/p junctions and from 7.8% to 8.8% for p/n junctions. This electrical passivation of the surface, most likely by removal of dangling bonds, is reflected in a higher shunt resistance in the J-V measurements. Monolayers of 1,8-nonadiyne were still reactive for click chemistry with a model catalyst, thus enabling simultaneous passivation and future catalyst coupling.