Mitigating Damage to Hybrid Perovskites Using Pulsed-Beam TEM.

Using a pulsed-beam transmission electron microscope, we discover a reduction in damage to methylammonium lead iodide (MAPbI3) as compared to conventional beams delivered at the same dose rates. For rates as low as 0.001 e·Å-2·s-1, we find up to a 17% reduction in damage at a total dose of 10 e·Å-2. We systematically study the effects of number of electrons in each pulse and the duration between pulse arrival. Damage increases for both, though the number of electrons per pulse has a larger effect. A crossover is identified, where a pulsed beam causes more damage than a conventional one. Although qualitatively similar to previous findings, the degree to which damage is reduced in MAPbI3 is less than that observed for other materials (e.g., C36H74), supporting the hypothesis that the effects are material- and damage-mechanism-dependent. Despite this, the observation here of damage reduction for relatively large electron packets (up to 200 electrons per pulse) suggests that MAPbI3 is in fact less susceptible to irradiation than C36H74, which may be related to reported self-healing effects. This work provides insights into damage processes and durability in hybrid perovskites and also illustrates the viability of using pulsed-beam TEM to explore the associated molecular-level routes to degradation, analogous to laser-accelerated energetic pulsed electron beams and the study of damage to biomolecules, cells, and tissues in radiobiology.

Formation of aligned periodic patterns during the crystallization of organic semiconductor thin films.

Self-organizing patterns with micrometre-scale features are promising for the large-area fabrication of photonic devices and scattering layers in optoelectronics. Pattern formation would ideally occur in the active semiconductor to avoid the need for further processing steps. Here, we report an approach to form periodic patterns in single layers of organic semiconductors by a simple annealing process. When heated, a crystallization front propagates across the film, producing a sinusoidal surface structure with wavelengths comparable to that of near-infrared light. These surface features initially form in the amorphous region within a micrometre of the crystal growth front, probably due to competition between crystal growth and surface mass transport. The pattern wavelength can be tuned from 800 nm to 2,400 nm by varying the film thickness and annealing temperature, and millimetre-scale domain sizes are obtained. This phenomenon could be exploited for the self-assembly of microstructured organic optoelectronic devices.