Development of smart molecularly imprinted tetrahedral amorphous carbon thin films for in vitro dopamine sensing
Giorgia Rinaldi, Khadijeh Nekoueian, Jarkko Etula, Tomi Laurila
Abstract
• Ultra-sensitive dopamine sensor created by combining molecular imprinting on ta-C thin films. • ta-C films on silicon wafers made via FCVA and coated with dopamine-imprinted polymers (MIPs). • ta-C/MIP sensors show high sensitivity to dopamine at physiologically relevant levels. • Process compatible with standard microsystem technology, enabling advanced integration. This study investigates how varying the thickness of tetrahedral amorphous carbon (ta-C) thin films and incorporating a titanium adhesion layer influences the structural and electrochemical properties of molecularly imprinted ta-C thin film-based sensing platforms, aiming to develop a molecularly imprinted ta-C electrochemical sensor for dopamine (DA) detection with physiologically relevant sensitivity. This electrochemical sensing platform was designed by integrating ta-C with molecularly imprinted polymers (MIPs). The process involved depositing a ta-C thin film onto boron-doped p-type silicon wafers through a filtered cathodic vacuum arc (FCVA) system. Subsequently, the ta-C sensing platforms were electrochemically coated with the MIP layer (DA-imprinted polypyrrole). We evaluated three configurations: (i) a 15 nm ta-C layer, (ii) a 7 nm ta-C layer with a 20 nm titanium adhesion layer, and (iii) a 15 nm ta-C layer with a 20 nm titanium adhesion layer. Comprehensive structural and electrochemical characterization was performed to understand how these modifications affect sensor performance. The optimized MIP/ta-C sensor demonstrated a sensitivity of 0.16 μA μM −1 cm −2 and a limit of detection (LOD) of 48.6 nM, suitable for detecting DA at physiological levels. Leveraging the synergistic effects of ta-C coatings and molecular imprinting, as well as its compatibility with common complementary metal–oxide–semiconductor (CMOS) processes underlines its potential for integration into microanalytical systems, paving the way for miniaturized and high-throughput sensing platforms.