Boosting the piezoelectric coefficients of flexible dynamic strain sensors made of chemically-deposited ZnO nanowires using compensatory Sb doping

The piezoelectric devices made of ZnO nanowires have received a great interest in the past decade as potential nanogenerators and sensors. However, their characteristics are still limited significantly by the screening of the piezoelectric potential generated under mechanical solicitations, originating from the high density of free electrons in ZnO nanowires. In order to tackle that issue, we develop the compensatory Sb doping of ZnO nanowires grown by chemical bath deposition, both in the low- and high-pH regions using Sb glycolate and ammonia as chemical additives. The adsorption process of Sb(III) species on the positively charged surfaces of ZnO nanowires proceeds through attractive electrostatic forces, resulting in the significant incorporation of Sb dopants with an atomic ratio in the range of 0.11-0.45%. The optical properties of Sb-doped ZnO nanowires exhibit additional phonon modes related to Sb dopants in the range of 500-750 cm-1 in the Raman spectra, and some specific characteristics in the nature and intensity of radiative recombination in the cathodoluminescence spectra. Importantly, the integration of Sb-doped ZnO nanowires encapsulated in PMMA and grown on PDMS into flexible piezoelectric dynamic strain sensors is shown to drastically boost the piezoelectric charge and voltage coefficients by a factor of 2.65 and 1.91, following the significant incorporation of Sb dopants. A subsequent thermal annealing under oxygen atmosphere is revealed to further increase the piezoelectric charge and voltage coefficients by an additional factor of 1.38 and 1.49, following the activation of Sb doping and engineering of hydrogen-related defects. Two figures-of-merit are eventually derived from the piezoelectric charge and voltage coefficients and their values for flexible piezoelectric composites made of annealed Sb-doped ZnO nanowires are compared to more conventional piezoelectric materials, showing their high potential for medical devices. The present findings highlight the strategy consisting in simultaneously introducing compensatory acceptors and engineering hydrogen-related defects to reduce the screening effect, representing an additional powerful way to enhance the characteristics of the piezoelectric devices integrating ZnO nanowires.