Structural origin of fracture-induced surface charges in piezoelectric pharmaceutical crystals for engineering bulk properties

Abstract

Altering surface chemistry of functional materials is an attractive route to enable large property enhancements without sacrificing overall structural-order, appealing to diverse fields of application sciences; however, the same remains unexplored for organic crystalline materials. Herein, piezoelectricity in pharmaceutical crystals is reported to show colossal surface charges driven by mechanical fracture — where a collection of dipoles arranged in polar head-to-tail fashion generates opposite surface charges on freshly fractured faces — causing them to actuate large distances over 75 µm in milliseconds. Kelvin probe force microscopy is leveraged to show many-fold surface potential enhancement in fractured surfaces relative to the pristine crystals. Further, complementarity of the surface potentials in a pair of fractured crystal shards and asymptotic decay behaviour with time are observed. Newly formed surfaces of the pharmaceutical crystals show long-lasting charges despite their relatively lower piezo-response confirmed by bulk piezometry. To establish the generality of surface phenomena, statistical analyses (≈50 samples) of post-fracture-attraction behaviour of crystals are performed. Finally, the application of fracture-driven surface charges in industrial processes is achieved by investigating flow-property and tablet-strength of bulk pharmaceutical materials. This multiscale approach unveils the symmetry-dependency of surface charges in fractured materials, and probes the same for utilisation in bulk-property engineering. © The Author(s) 2025.