In recent decades, many technological advances have been enabled by nanoscale phenomena, giving rise to the field of nanotechnology. In particular, unique optical and electronic phenomena occur on length scales less than 10 nanometres, which enable novel applications. Halide perovskites have been the focus of intense research on their optoelectronic properties and have demonstrated impressive performance in photovoltaic devices and later in other optoelectronic technologies, such as lasers and light-emitting diodes. The most studied crystalline form is the three-dimensional one, but, recently, the exploration of the low-dimensional derivatives has enabled new sub-classes of halide perovskite materials to emerge with distinct properties. In these materials, low-dimensional metal halide structures responsible for the electronic properties are separated and partially insulated from one another by the (typically organic) cations. Confinement occurs on a crystal lattice level, enabling bulk or thin-film materials that retain a degree of low-dimensional character. In particular, quasi-zero dimensional perovskite derivatives are proving to have distinct electronic, absorption, and photoluminescence properties. They are being explored for various technologies beyond photovoltaics (e.g. thermoelectrics, lasing, photodetectors, memristors, capacitors, LEDs). This review brings together the recent literature on these zero-dimensional materials in an interdisciplinary way that can spur applications for these compounds. The synthesis methods, the electrical, optical, and chemical properties, the advances in applications, and the challenges that need to be overcome as candidates for future electronic devices have been covered.

Lead halide perovskites have been revolutionary in the last decade in many optoelectronic sectors. Their bismuth-based counterparts have been considered a good alternative thanks to their composition of earth-abundant elements, good chemical stability, and low toxicity. Moreover, their electronic structure is in a quasi-zero-dimensional (0D) configuration, and they have recently been explored for use beyond optoelectronics. A significant limitation in applying thin-film technology is represented by the difficulty of synthesizing compact layers with easily scalable methods. Here, the engineering of a two-step synthesis in an air of methylammonium bismuth iodide compact thin films is reported. The critical steps of the process have been highlighted so that the procedure can be adapted to different substrates and application areas.

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The prototypical chalcogenide perovskite BaZrS3, with its direct band gap, exceptionally strong light-harvesting ability and good carrier transport properties, provides fundamental prerequisites for a promising photovoltaic material. This inspired synthesis of BaZrS3 in the form of thin films, using sputtering and rapid thermal processing, aimed at device fabrication for future optoelectronic applications. Using a combination of long- and short-range structural information from x-ray absorption spectroscopy (XAS) and x-ray diffraction (XRD), we have elucidated how, starting from a random network of Ba, Zr, S atoms, thermal treatment induces crystallization and growth of BaZrS3 and explained its impact on observed PL properties. We also provide an electronic structure description and confirm the surface material chemistry using a combination of depth-dependent Photoelectron Spectroscopy (PES) using Hard X-ray (HAXPES) and traditional Al Kα radiation. From the knowledge of the optical band gap of BaZrS3 thin films, synthesized at an optimal temperature of 900°C, and our estimation of the valence band edge position with respect to the Fermi level, one may conclude that these semiconductor films are intrinsic in nature with a slight n-type character. A detailed understanding of the growth mechanism and electronic structure of BaZrS3 thin films helps pave the way for their use in photovoltaics.