RESUMEN
The desire to commercialize perovskite solar cells continues to mount, motivating the development of scalable production. Evaluations of the impact of open-air processing have revealed a variety of physical changes in the fabricated devicesâwith few changes having the capacity to be functionalized. Here, we highlight the beneficial role of ambient oxygen during the open-air thermal processing of metastable γ-CsPbI3-based perovskite thin films and devices. Physiochemical-sensitive probes elucidate oxygen intercalation and the formation of Pb-O bonds in the CsPbI3 crystal, entering via iodine vacancies at the surface, creating superoxide (O2-) through electron transfer reactions with molecular oxygen, which drives the formation of a zero-dimensional Cs4PbI6 capping layer during annealing (>330 °C). The chemical conversion permanently alters the film structure, helping to shield the subsurface perovskite from moisture and introduces lattice anchoring sites, stabilizing otherwise unstable γ-CsPbI3 films. This functional modification is demonstrated in γ-CsPbI2Br perovskite solar cells, boosting the operational stability and photoconversion efficiency of champion devices from 12.7 to 15.4% when annealed in dry air. Such findings prompt a reconsideration of glovebox-based perovskite solar cell research and establish a scenario where device fabrication can in fact greatly benefit from ambient oxygen.
RESUMEN
The black perovskite phase of CsPbI3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI2-based interfacial microstructure into otherwise-unstable CsPbI3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and exhibit enhanced long-term stability of the black phase (beyond 2.5 years in a dry environment), due to increasing the phase transition energy barrier and limiting the spread of potential yellow phase formation to structurally isolated domains of the grid. This stabilizing effect is readily achieved at the device level, where unencapsulated CsPbI3 perovskite photodetectors display ambient-stable operation. These findings provide insights into the nature of phase destabilization in emerging CsPbI3 perovskite devices and demonstrate an effective stabilization procedure which is entirely orthogonal to existing approaches.
RESUMEN
We demonstrate a simple and effective approach to control the diameter of ultrathin ZnO nanowires with high aspect ratios and high densities over large areas. Diblock copolymer-based nanoparticle arrays exhibiting a high degree of hexagonal order and offering easy control of particle size (typically 1-10 nm) and interparticle spacing (25-150 nm) are utilized as nanocatalysts for the subsequent growth of semiconductor nanowires. The as-grown ZnO nanowires exhibit a single crystal hexagonal wurtzite structure and grow along the [0002] direction. Facetted catalyst particles were observed at the tip of the nanowires after synthesis, thus suggesting a catalyst-assisted vapor-solid-solid (VSS) rather than a vapor-liquid-solid (VLS) growth mechanism, the latter being frequently used in semiconductor nanowire production. Such a growth process allows us to easily prepare ultrathin ZnO nanowires with tunable diameters well below 10 nm by taking advantage of the inherent size control of the micellar method during deposition of the catalyst nanoparticles. Raman spectroscopy reveals a phonon confinement effect as the diameter of nanowires decreases. Photoluminescence spectra of these ultrathin nanowires indicate a blue shift of the free excitons and their phonon replicas by 37 meV induced by quantum confinement.