Nano- and Microstructured Copper/Copper Oxide Composites on Laser-Induced Carbon for Enzyme-Free Glucose Sensors

Low-cost enzyme-free glucose sensors with partial flexibility adaptable for wearable Internet of Things devices that can be envisioned as personalized point-of-care devices were produced by electroplating copper on locally carbonized flexible meta-polyaramid (Nomex) sheets using laser radiation. Freestanding films were annealed in nitrogen and nitrogen/air working environments, leading to the formation of Cu microspheroids and CuO urchins dispersed on the substrate film. The aggregation mechanism, crystallographic properties, surface chemistry, and electrochemical properties of the films were studied using scanning electron microscopy, X-ray diffractometry, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. Cu microspheroids and CuO urchins attained activity for glucose detection and showed improvement of amperometric sensitivity to 0.25 and 0.32 mA cm$^{–2}$ mM$^{–1}$, respectively. The CuO urchin film retained its chemical composition after amperometric testing, and, by rinsing, allowed multiple repetitions with reproducible results. This study opens the possibility for the fabrication of durable composite biosensors with tailored shape, capable of implementation in flexible carriers, and microfluidic systems.