Microplasma direct writing for site-selective surface functionalization of carbon microelectrodes

Aung Thiha; Fatimah Ibrahim; Shalini Muniandy; Marc J Madou

doi:10.1038/s41378-019-0103-0

Microplasma direct writing for site-selective surface functionalization of carbon microelectrodes

Microsyst Nanoeng. 2019 Nov 18:5:62. doi: 10.1038/s41378-019-0103-0. eCollection 2019.

Authors

Aung Thiha^{1

2}, Fatimah Ibrahim^{1

2}, Shalini Muniandy^{2

3}, Marc J Madou^{1

2

4

5}

Affiliations

¹ 1Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia.
² 2Centre for Innovation in Medical Engineering (CIME), Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia.
³ 3Nanotechnology and Catalysis Research Centre, Institute of Graduate Studies, University of Malaya, 50603 Kuala Lumpur, Malaysia.
⁴ 4Department of Biomedical Engineering, University of California, Irvine, CA 92697 USA.
⁵ 5Department of Mechanical and Aerospace Engineering, University of California, Irvine, CA 92697 USA.

Abstract

Carbon micro- and nanoelectrodes fabricated by carbon microelectromechanical systems (carbon MEMS) are increasingly used in various biosensors and supercapacitor applications. Surface modification of as-produced carbon electrodes with oxygen functional groups is sometimes necessary for biofunctionalization or to improve electrochemical properties. However, conventional surface treatment methods have a limited ability for selective targeting of parts of a surface area for surface modification without using complex photoresist masks. Here, we report microplasma direct writing as a simple, low-cost, and low-power technique for site-selective plasma patterning of carbon MEMS electrodes with oxygen functionalities. In microplasma direct writing, a high-voltage source generates a microplasma discharge between a microelectrode tip and a target surface held at atmospheric pressure. In our setup, water vapor acts as an ionic precursor for the carboxylation and hydroxylation of carbon surface atoms. Plasma direct writing increases the oxygen content of an SU-8-derived pyrolytic carbon surface from ~3 to 27% while reducing the carbon-to-oxygen ratio from 35 to 2.75. Specifically, a microplasma treatment increases the number of carbonyl, carboxylic, and hydroxyl functional groups with the largest increase observed for carboxylic functionalities. Furthermore, water microplasma direct writing improves the hydrophilicity and the electrochemical performance of carbon electrodes with a contact-angle change from ~90° to ~20°, a reduction in the anodic peak to cathodic peak separation from 0.5 V to 0.17 V, and a 5-fold increase in specific capacitance from 8.82 mF∙cm^-2 to 46.64 mF∙cm^-2. The plasma direct-writing technology provides an efficient and easy-to-implement method for the selective surface functionalization of carbon MEMS electrodes for electrochemical and biosensor applications.

Keywords: Biosensors; Chemistry; Electrical and electronic engineering; Structural properties.