Three-dimensional (3D) printing technology has emerged
as a powerful
technology for the fabrication of low-cost microfluidics. Nevertheless,
the fabrication of microfluidic devices integrating high-performance
electrochemical sensors in practical applications is still an open
challenge. Although automatic fabrication of the microfluidic device
and the electrodes can be successfully carried out using a one-step
multimaterial fused filament fabrication (FFF) approach, the as-printed
electrochemical performance of these electrodes is not good enough
for chemical (bio)sensing and their surface modification is challenging
because after closing the channel there is no physical access to the
electrode. Thus, here a pause–print–pause (PPP) microfabrication
approach was implemented. The fabrication was paused before printing
the microfluidics, and the filament-based electrodes were directly
modified on the printing bed via stencil printing, drop casting, and
electrodeposition. To exemplify this versatile workflow, the design
of a microfluidic glucose sensor was proposed. To this end, first,
the working and counter electrodes were stencil printed with graphite
ink while the reference electrode was stencil printed with Ag|AgCl
ink. Then, Prussian blue was formed on the working electrode either
by drop casting or by electrodeposition, and glucose oxidase was drop
cast on top. At this point, the microfabrication process was resumed,
and the microfluidics were printed on top of the modified electrodes
to complete the construction of hybrid electrochemical fluidic fused
filament fabricated devices (h-eF
4
Ds). This print–pause–print
approach is not limited to ink-based electrodes or glucose oxidase,
and we envisage these results will pave the way for the effective
integration of electrodes in microfluidic devices in a simple and
clean-room-free approach, allowing the development of highly customized
eF
4
Ds for a plethora of analytes with high significance.