Atomic layer deposition is widely acknowledged as a powerful technique for the deposition of high quality layers for several applications including photovoltaics (PV). The capability of ALD to generate dense, conformal, virtually pinhole-free layers becomes attractive also for the emerging organo-metal halide perovskite solar cells (PSCs), which have garnered the interest of the PV community through their remarkable efficiency gains, now over 20%, in just a few years of research. Until now, the application of ALD layers in PSCs has almost exclusively been restricted to the stages of device fabrication prior to perovskite deposition. Researchers have mainly focused on fabricating efficient electron and hole transport layers (TiO₂, SnO₂, ZnO, NiO) and ultra-thin Al₂O₃ or TiO₂ passivation layers for several device configurations. The first section of this contribution reviews the current state-of-the-art ALD for perovskite solar cells. Then, we explore other potential opportunities, such as the fabrication of doped metal oxide selective contacts and transparent electrodes, also for use in tandem solar cell architectures, as well as barrier layers for encapsulation. Finally, we present our own experimental investigation of the challenges involved in depositing directly on perovskite absorbers in view of replacing organic electron and hole transport layers with ALD metal oxides (MOs). Therefore, the effects of temperature, oxidizing agents and metal precursors on perovskite are studied. A number of insights are gained which can lead to the development of ad hoc ALD processes that are compatible with the underlying perovskite, in this case, methylammonium lead iodide, MAPbI₃. The phase purity and surface chemistry of the perovskite were used as metrics to quantify the feasibility of depositing selected MOs which can be adopted as selective contacts and passivation layers.

The ability to grow inorganic thin films with highly controllable structural and optical properties at low substrate temperature enables the manufacturing of functional devices on thermo-sensitive substrates without the need of material postprocessing. In this study, the authors report on the growth of zinc oxide films by direct plasma-enhanced atomic layer deposition at near room temperature. Diethyl zinc and oxygen plasma were used as the precursor and coreactant, respectively. The process was optimized with respect to the precursor and coreactant dosing as well as to the purging times, which ultimately resulted in saturated atomic layer deposition growth. The so-obtained films exhibit a polycrystalline pattern with a (100) texture and low amount of incorporated carbon. Furthermore, the possibility to tune crystallite size, refractive index, and bandgap of the films by adapting the plasma radio-frequency power is demonstrated.

The chemical vapor deposition (CVD) polymerization of metalloporphyrin building units is demonstrated to provide an easily up-scalable one-step method toward the deposition of a new class of dense and defect-free metal–organic covalent network (MOCN) layers. The resulting hyper-thin and flexible MOCN layers exhibit outstanding gas-separation performances for multiple gas pairs.