Laser-Induced Periodic Surface Structures (LIPSS) on Heavily Boron-Doped Diamond for Electrode Applications

ACS Appl Mater Interfaces. 2018 Dec 12;10(49):43236-43251. doi: 10.1021/acsami.8b15951. Epub 2018 Nov 29.

Abstract

Diamond is known as a promising electrode material in the fields of cell stimulation, energy storage (e.g., supercapacitors), (bio)sensing, catalysis, etc. However, engineering its surface and electrochemical properties often requires costly and complex procedures with addition of foreign material (e.g., carbon nanotube or polymer) scaffolds or cleanroom processing. In this work, we demonstrate a novel approach using laser-induced periodic surface structuring (LIPSS) as a scalable, versatile, and cost-effective technique to nanostructure the surface and tune the electrochemical properties of boron-doped diamond (BDD). We study the effect of LIPSS on heavily doped BDD and investigate its application as electrodes for cell stimulation and energy storage. We show that quasi-periodic ripple structures formed on diamond electrodes laser-textured with a laser accumulated fluence of 0.325 kJ/cm2 (800 nm wavelength) displayed a much higher double-layer capacitance of 660 μF/cm2 than the as-grown BDD (20 μF/cm2) and that an increased charge-storage capacity of 1.6 mC/cm2 (>6-fold increase after laser texturing) and a low impedance of 2.74 Ω cm2 turn out to be appreciable properties for cell stimulation. Additional morphological and structural characterization revealed that ripple formation on heavily boron-doped diamond (2.8 atom % [B]) occurs at much lower accumulated fluences than the 2 kJ/cm2 typically reported for lower doping levels and that the process involves stronger graphitization of the BDD surface. Finally, we show that the exposed interface between sp2 and sp3 carbon layers (i.e. the laser-ablated diamond surface) revealed faster kinetics than the untreated BDD in both ferrocyanide and RuHex mediators, which can be used for electrochemical (bio)sensing. Overall, our work demonstrates that LIPSS is a powerful single-step tool for the fabrication of surface-engineered diamond electrodes with tunable material, electrochemical, and charge-storage properties.

Keywords: LIPSS; boron-doped diamond; charge-storage capacity; cyclic voltammetry; impedance spectroscopy; laser texturing; ripples; supercapacitor.