A dual-functional flexible sensor based on defects-free Co-doped ZnO nanorods decorated with CoO clusters towards pH and glucose monitoring of fruit juices and human fluids

Abstract

Herein, ZnO nanorods were doped with Co and decorated with CoO clusters through an in situ technique to create a CoO/Co-doped ZnO (CO/CZO) heterostructure at low temperatures (150 °C) on a flexible PET substrate. In the CO/CZO heterostructure, the Co dopant has a low energy barrier to substitute Zn atoms and adsorb over oxygen atoms and their vacancies. Therefore, it decreased the charge density (N_D = 2.64 × 10¹⁹ cm⁻³) on non-active sites of ZnO and lowered the charge transfer resistance (317 Ω) at Co-doped-ZnO/electrolyte interface by suppressing the native defects and reducing the Schottky barrier height (− 0.35 eV), respectively. Furthermore, CoO clusters induced a p-n heterostructure with Co-doped ZnO, prevented corrosion, increased the active sites for analyte absorption, and increased the ultimate tensile strength (4.85 N m⁻²). These characteristics enabled the CO/CZO heterostructure to work as a highly sensitive, chemically stable, and flexible pH and glucose oxidation electrode. Therefore, CO/CZO heterostructure was explored for pH monitoring in human fluids and fruit juices, demonstrating a near-Nernst-limit pH sensitivity (52 mV/pH) and fast response time (19 s) in each human fluid and fruit juice. Also, it demonstrated high sensitivity (4656 µM mM⁻¹ cm⁻²), low limit of detection (0.15 µM), a broad linear range (0.04 mM to 8.85 mM) and good anti-interference capacity towards glucose-sensing. Moreover, it demonstrated excellent flexibility performances, retained 53% and 69% sensitivity of the initial value for pH and glucose sensors, respectively, after 500 bending, stretching, and warping cycles.

Highlights

Low-temperatures growth of defect-free CoO/Co-doped ZnO heterostructure.

Doping lowered N_D on non-active sites, ɸ_B, and R_ct at ZnO/electrolyte interface.

CoO prevent corrosion, increase active sites and enhance ultimate tensile strength.

Obtained high sensitivity 52 mV/pH for pH and 4656 µM mM⁻¹ cm⁻² for glucose sensors

Both potentiometric and amperometric mechanism of the heterostructure is proposed.