Black phosphorus (BP) is an elemental layered material with a strong in-plane anisotropic structure. This anisotropic structure is accompanied by anisotropic optical, electrical, thermal, and mechanical properties. Despite interest in BP from both fundamental and technical aspects, investigation into the structural dynamics of BP caused by strain fields, which are prevalent for two-dimensional (2D) materials and tune the material physical properties, has been overlooked. Here, we report the morphological dynamics of photoexcited BP membranes observed using time-resolved diffractograms and dark-field images obtained via ultrafast electron microscopy. Aided by 4D reconstruction, we visualize the nonequilibrium bulging of thin BP membranes and reveal the buckling transition driven by impulsive thermal stress upon photoexcitation in real time. The bulging, buckling, and flattening (on strain release) showed anisotropic spatiotemporal behavior. Our observations offer insights into the fleet

Black phosphorus (BP) is an elemental layered material with a strong in-plane anisotropic structure. This anisotropic structure is accompanied by anisotropic optical, electrical, thermal, and mechanical properties. Despite interest in BP from both fundamental and technical aspects, investigation into the structural dynamics of BP caused by strain fields, which are prevalent for two-dimensional (2D) materials and tune the material physical properties, has been overlooked. Here, we report the morphological dynamics of photoexcited BP membranes observed using time-resolved diffractograms and dark-field images obtained via ultrafast electron microscopy. Aided by 4D reconstruction, we visualize the nonequilibrium bulging of thin BP membranes and reveal the buckling transition driven by impulsive thermal stress upon photoexcitation in real time. The bulging, buckling, and flattening (on strain release) showed anisotropic spatiotemporal behavior. Our observations offer insights into the fleeting morphology of anisotropic 2D matter and give a glimpse into the mapping of transient, modulated physical properties upon impulsive excitation, as well as strain engineering at the nanoscale