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Materials Science in Additive Manufacturing                              Materials for 3D-printed electrodes



            and human clinical devices. For example, Utah electrodes   stability and processability by modification [60-62] . Thus,
            and Michigan electrodes  use  metal  as conductors   metal nanomaterials become the preferred materials for 3D
            and are utilized as invasive electrodes for intracranial   printing of flexible electrodes for medical applications. In
            applications [46,47] . Nevertheless, conventional hard metals   another study, Im et al. added multifunctional thiols to AuNP
            are often subjected to mechanical mismatches at biological   ink to modulate the cohesion of AuNP by inducing strong
            tissue interfaces, resulting in irreversible damage and   interactions between the thiol groups and the gold surface
            inflammatory reactions [48-51] . These issues greatly limit   so that microcracks and pores are not easily generated in
            the use of metal electrodes in animal research and human   the AuNP film after heat exposure (Figure  3C) . The
                                                                                                       [11]
            clinical neurological recording devices.           modified AuNP ink is more structurally stable during
              Recent years have seen the emergence of several   processing and can form stable, flexible conductive devices
            strategies for combining flexible polymer materials   by IJP onto flexible substrates. These flexible electrodes
            with metallic materials, effectively mitigating the   are stable in high humidity and salt-rich liquids and can
            abovementioned problems. Hui et al prepared an Ag-based   maintain stable conductivity after more than 1,000 bending
                                                                       [11]
            ink for extruded 3D printing by mixing silver with hydrogel   cycle tests . The improvements of the ink properties are
            and showed that the ink can be printed in a hydrogel-  made possible only after the tremendous advancements in
            support  matrix  to form  a  3D conductive  structure  that   materials science, which further spawn the development of
            can be stretched and compressed . Electronic devices   various flexible and elastomeric materials with mechanical
                                        [52]
            prepared in this way can be used as biomedical electrodes.   properties equivalent to those of human tissues and organs,
            Ma et al. reported the optimization of a drop-on-demand,   and lay solid foundation for preparing flexible medical
            high-resolution electrohydrodynamic-based jet-printing   electrodes based on metal materials.
            method for generating 3D gold (Au) micropillar electrode   In  addition to the  traditional solid  metal,
            arrays on flexible substrates (Figure 3A) . The electrode   room-temperature liquid metals represented by gallium
                                            [53]
            array showed mechanical flexibility under planar, concave,   (Ga)-based alloys have good room-temperature mobility
            and convex conditions, and its sensing capability remained   and low toxicity. The liquid metals can reach a conductivity
            virtually unchanged . Another study  conducted  by  a   of 3.8 × 10  S/m, making them ideal materials for
                                                                          6
                            [53]
            research team from Carnegie Mellon University reported   manufacturing flexible electrodes [63,64] . However, it is still
            the  formation of  shanks  with  a diameter  of  only  a  few   challenging for liquid metals to form a continuous and stable
            tens of micrometers by stacking atomized metal ink as   conductive structure due to their highly oxidizable surface,
            an aerosol on a two-dimensional (2D) substrate. A high-  large surface tension, and low viscosity [65-67] . Wu  et  al.
            density microarray electrode with 2,600 shanks per square   printed liquid metal in an acrylamide/nanoclay support
            centimeter was obtained. This microarray electrode caused   bath with oxidizing properties, forming a viscoelastic
            very minimal gross tissue damage and yielded an excellent   oxide skin instantaneously on the extruded liquid metal
            signal-to-noise  ratio  given  the  low  impedance  of  the   surface . It allows the formation of continuous liquid
                                                                     [67]
            metal ink . On the other hand, Morgan et al. attempted   metal filaments (150 μm) with tensile strains up to 1400%,
                    [54]
            to integrate 3D microarrays on flexible polyimide or   as shown in  Figure  3D . This flexible electrode can be
                                                                                  [67]
            parylene  C films through two-photon lithography and   used as a strain sensor and a passive resonant sensor, which
            modify the metallic platinum on arrays to obtain flexible   has potential applications in wearable biomonitoring
            microarray  electrodes .  The  microarray  electrode  with   and untethered robotics. In addition, a common method
                              [55]
            flexible  substrates  significantly  reduces  tissue  damage   for fabricating flexible electrodes based on liquid metals
            caused by hard metals. This electrode can be used for signal   involves the preparation of liquid metals into nano-sized
            acquisition inside tissues to enhance the spatial resolution   particles, followed by printing and molding through
            of physiological electrical signals and hold immense   annealing or other operations [68-70] .
            promise for use as implantable brain-computer interfaces.  This section summarizes the research on metallic
              Compared to common metals, metal nanoparticles   materials  used  in  the  preparation  of  3D-printed  flexible
            (NPs)/nanowires/nanosheets have relatively small sizes   medical electrodes. These studies have facilitated flexible
            and more interactions between grains [56-58] . A  recent   metal-based electrodes in implantable neural interfaces,
            study used CuO NP inks for electrospinning, as shown in   sensors, and wearable devices by improving 3D printing
            Figure 3B. After post-processing, a Cu wire with a width   techniques or modifying the materials. The involved
            of 50 μm, a thickness of 1.48 μm and a resistivity of only   methods not only allow better machinability while
            5.46  μΩ·cm was obtained . Moreover, the high surface   maintaining the good properties of the metallic material
                                 [59]
            area to volume ratio of metal nanomaterials allows them   but also increase the mechanical properties of the flexible
            to adsorb small molecules to achieve better chemical   electrodes, such as tensile and flexibility.


            Volume 2 Issue 4 (2023)                         4                       https://doi.org/10.36922/msam.2084
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