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A quantitative understanding of the nanoscale piezoelectric property will unlock many application potentials of the electromechanical coupling phenomenon under quantum confinement. In this work, we present an atomic force microscopy- (AFM-) based approach to the quantification of the nanometer-scale piezoelectric property from single-crystalline zinc oxide nanosheets (NSs) with thicknesses ranging from 1 to 4 nm. By identifying the appropriate driving potential, we minimized the influences from electrostatic interactions and tip-sample coupling, and extrapolated the thickness-dependent piezoelectric coefficient ( d  33 ). By averaging the measured  d  33  from NSs with the same number of unit cells in thickness, an intriguing tri-unit-cell relationship was observed. From NSs with 3 n  unit cell thickness ( n  = 1, 2, 3), a bulk-like  d  33  at a value of ~9 pm/V was obtained, whereas NSs with other thickness showed a ~30% higher  d  33  of ~12 pm/V. Quantification of  d  33  as a function of ZnO unit cell numbers offers a new experimental discovery toward nanoscale piezoelectricity from nonlayered materials that are piezoelectric in bulk.

Thickness-Dependent Piezoelectric Property from Quasi-Two-Dimensional Zinc Oxide Nanosheets with Unit Cell Resolution