From Chaos to Control: Programmable Crack Patterning with Molecular Order in Polymer Substrates.

Cracks are typically associated with the failure of materials. However, cracks can also be used to create periodic patterns on the surfaces of materials, as observed in the skin of crocodiles and elephants. In synthetic materials, surface patterns are critical to micro- and nanoscale fabrication processes. Here, a strategy is presented that enables freely programmable patterns of cracks on the surface of a polymer and then uses these cracks to pattern other materials. Cracks form during deposition of a thin film metal on a liquid crystal polymer network (LCN) and follow the spatially patterned molecular order of the polymer. These patterned sub-micrometer scale cracks have an order parameter of 0.98 ± 0.02 and form readily over centimeter-scale areas on the flexible substrates. The patterning of the LCN enables cracks that turn corners, spiral azimuthally, or radiate from a point. Conductive inks can be filled into these oriented cracks, resulting in flexible, anisotropic, and transparent conductors. This materials-based processing approach to patterning cracks enables unprecedented control of the orientation, length, width, and depth of the cracks without costly lithography methods. This approach promises new architectures of electronics, sensors, fluidics, optics, and other devices with micro- and nanoscale features.

Sputtered ruthenium oxide coatings for neural stimulation and recording electrodes.

We have investigated the deposition and electrochemical properties of sputtered ruthenium oxide coatings for neural stimulation and recording electrodes. A combination of oxygen and water vapor was used as a reactive gas mixture during DC magnetron sputtering from a ruthenium metal target. The sputtering plasma was monitored by optical emission spectroscopy to determine the reactive species present and confirm the control of plasma chemistry by reactive gas flow rates into the deposition chamber. The effect of the O2 :H2 O gas ratio on the microstructure and electrochemical properties of the ruthenium oxide were studied in detail. We employed a combination of surface characterization techniques, including scanning electron microscopy, x-ray diffraction, and x-ray photoelectron spectroscopy, to understand the relationship between plasma chemistry and the microstructure of the films produced under different gas flow conditions. Electrochemical characterization included cyclic voltammetry, electrochemical impedance spectroscopy, and voltage transient measurements, performed on planar ruthenium oxide electrodes with a geometric surface area of 1960 µm2 . At an O2 :H2 O gas flow rate ratio of 1:3, a cathodal charge-storage capacity per unit film thickness of 228.7 mC cm-2 µm-1 (median, Q1 = 134.5, Q3 = 236.6, n = 15) and a charge-injection capacity (0.6 V anodal interpulse bias) of 7.4 mC cm-2 (median, Q1 = 6.9, Q3 = 8.3, n = 15) were obtained in phosphate buffered saline. The charge-injection capacity of ruthenium oxide sputtered with water vapor in the reactive plasma is comparable with sputtered iridium oxide (SIROF) and higher than reported values for porous TiN, a commonly employed high-surface area stimulation electrode coating.

Deployable, liquid crystal elastomer-based intracortical probes.

Intracortical microelectrode arrays (MEAs) are currently limited in their chronic functionality due partially to the foreign body response (FBR) that develops in regions immediately surrounding the implant (typically within 50-100 µm). Mechanically flexible, polymer-based substrates have recently been explored for MEAs as a way of minimizing the FBR caused by the chronic implantation. Nonetheless, the FBR degrades the ability of the device to record neural activity. We are motivated to develop approaches to deploy multiple recording sites away from the initial site of implantation into regions of tissue outside the FBR zone. Liquid Crystal Elastomers (LCEs) are responsive materials capable of programmable and reversible shape change. These hydrophobic materials are also non-cytotoxic and compatible with photolithography. As such, these responsive materials may be well suited to serve as substrates for smart, implantable electronics. This study explores the feasibility of LCE-based deployable intracortical MEAs. LCE intracortical probes are fabricated on a planar substrate and adopt a 3D shape after being released from the substrate. The LCE probes are then fixed in a planar configuration using polyethylene glycol (PEG). The PEG layer dissolves in physiological conditions, allowing the LCE probe to deploy post-implantation. Critically, we show that LCE intracortical probes will deploy within a brain-like agarose tissue phantom. We also show that deployment distance increases with MEA width. A finite element model was then developed to predict the deformed shape of the deployed probe when embedded in an elastic medium. Finally, LCE-based deployable intracortical MEAs were capable of maintaining electrochemical stability, recording extracellular signals from cortical neurons in vivo, and deploying recording sites greater than 100 µm from the insertion site in vivo. Taken together, these results suggest the feasibility of using LCEs to develop deployable intracortical MEAs. STATEMENT OF SIGNIFICANCE: Deployable MEAs are a recently developed class of neural interfaces that aim to shift the recording sites away from the region of insertion to minimize the negative effects of FBR on the recording performance of MEAs. In this study, we explore LCEs as a potential substrate for deployable MEAs. The novelty of this study lies in the systematic and programmable deployment offered by LCE-based intracortical MEAs. These results illustrate the feasibility and potential application of LCEs as a substrate for deployable intracortical MEAs.

Liquid crystal elastomers as substrates for 3D, robust, implantable electronics.

New device architectures favorable for interaction with the soft and dynamic biological tissue are critical for the design of indwelling biosensors and neural interfaces. For the long-term use of such devices within the body, it is also critical that the component materials resist the physiological harsh mechanical and chemical conditions. Here, we describe the design and fabrication of mechanically and chemically robust 3D implantable electronics. This is achieved by using traditional photolithography to pattern electronics on liquid crystal elastomers (LCEs), a class of shape programmable materials. The chemical durability of LCE is evaluated under accelerated in vitro conditions simulating the physiological environment; for example, LCE exhibits less than 1% mass change under a hydrolytic medium simulating >1 year in vivo. By employing twisted nematic LCEs as dynamic substrates, we demonstrate electronics that are fabricated on planar substrates but upon release morph into programmed 3D shapes. These shapes are designed to enable intrinsically low failure strain materials to be extrinsically stretchable. For example, helical multichannel cables for electrode arrays withstand cyclic stretching and buckling over 10 000 cycles at 60% strain while being soaked in phosphate-buffered saline. We envision that these LCE-based electronics can be used for applications in implantable neural interfaces and biosensors.

High-charge-capacity sputtered iridium oxide neural stimulation electrodes deposited using water vapor as a reactive plasma constituent.

The deposition and properties of sputtered iridium oxide films (SIROFs) using water vapor as a reactive gas constituent are investigated for their potential as high-charge-capacity neural stimulation electrodes. Systematic investigation through a series of optical and electrochemical measurements reveals that the incorporation of water vapor as a reactive gas constituent, along with oxygen, alters the reduction-oxidation (redox) state of the plasma as well as its morphology and the electrochemical characteristics, including the cathodal charge-storage capacity (CSCc ) and charge-injection capacity (CIC), of the SIROF. An apparent optimal O2 :H2 O gas ratio of 1:3 produced SIROF with a CSCc of 182.0 mC cm-2 µm-1 (median, Q1 = 172.5, Q3 = 193.4, n = 15) and a CIC of 3.57 mC cm-2 (median, Q1 = 2.97, Q3 = 4.58, n = 12) for 300-nm-thick films. These values are higher than those obtained with SIROFs deposited using no water vapor by a factor of 2.3 and 1.7 for the CSCc and CIC, respectively. Additionally, the SIROF showed minimal changes in electrochemical characteristics over 109 pulses of constant current stimulation and showed no indication of cytotoxicity toward primary cortical neurons in a cell viability assay. These results warrant investigation of the chronic recording and stimulation capabilities of the SIROF for implantable microelectrode arrays.

Responsive, 3D Electronics Enabled by Liquid Crystal Elastomer Substrates.

Traditional electronic devices are rigid, planar, and mechanically static. The combination of traditional electronic materials and responsive polymer substrates is of significant interest to provide opportunities to replace conventional electronic devices with stretchable, 3D, and responsive electronics. Liquid crystal elastomers (LCEs) are well suited to function as such dynamic substrates because of their large strain, reversible stimulus response that can be controlled through directed self-assembly of molecular order. Here, we discuss using LCEs as substrates for electronic devices that are flat during processing but then morph into controlled 3D structures. We design and demonstrate processes for a variety of electronic devices on LCEs including deformation-tolerant conducting traces and capacitors and cold temperature-responsive antennas. For example, patterning twisted nematic orientation within the substrate can be used to create helical electronic devices that stretch up to 100% with less than 2% change in resistance or capacitance. Moreover, we discuss self-morphing LCE antennas which can dynamically change the operating frequency from 2.7 GHz (room temperature) to 3.3 GHz (-65 °C). We envision applications for these 3D, responsive devices in wearable or implantable electronics and in cold-chain monitoring radio frequency identification sensors.

Chronic recording and electrochemical performance of amorphous silicon carbide-coated Utah electrode arrays implanted in rat motor cortex.

OBJECTIVE: Clinical applications of implantable microelectrode arrays are currently limited by device failure due to, in part, mechanical and electrochemical failure modes. To overcome this challenge, there is significant research interest in the exploration of novel array architectures and encapsulation materials. Amorphous silicon carbide (a-SiC) is biocompatible and corrosion resistant, and has recently been employed as a coating on biomedical devices including planar microelectrode arrays. However, to date, the three-dimensional Utah electrode array (UEA) is the only array architecture which has been approved by the food and drug administration (FDA) for long-term human trials. APPROACH: Here, we demonstrate, for the first time, that UEAs can be fabricated with a-SiC encapsulation and sputtered iridium oxide film (SIROF) electrode coatings, and that such arrays are capable of single-unit recordings over a 30 week implantation period in rat motor cortex. Over the same period, we carried out electrochemical measurements, including voltage transients, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS), to evaluate potential failure modes. Furthermore, we evaluated chronic foreign body response via fluorescence immunohistochemistry following device explantation. MAIN RESULTS: During the indwelling period, we observed a reduction in active electrode yield percentage from 94.6 ± 5.4 (week 1) to 16.4 ± 11.5% (week 30). While the average active electrode yield showed a steady reduction, it is noteworthy that 3 out of 8 UEAs recorded greater than 60% active electrode yield at all times through 24 weeks and 1 out of 8 UEAs recorded greater than 60% active electrode yield at all times through the whole implantation period. SIGNIFICANCE: In total, these findings further suggest that a-SiC may serve as a mechanically and electrochemically stable device encapsulation alternative to polymeric coatings such as Parylene-C.

Effect of oxidation on intrinsic residual stress in amorphous silicon carbide films.

The change in residual stress in plasma enhanced chemical vapor deposition amorphous silicon carbide (a-SiC:H) films exposed to air and wet ambient environments is investigated. A close relationship between stress change and deposition condition is identified from mechanical and chemical characterization of a-SiC:H films. Evidence of amorphous silicon carbide films reacting with oxygen and water vapor in the ambient environment are presented. The effect of deposition parameters on oxidation and stress variation in a-SiC:H film is studied. It is found that the films deposited at low temperature or power are susceptible to oxidation and undergo a notable increase in compressive stress over time. Furthermore, the films deposited at sufficiently high temperature (≥325 C) and power density (≥0.2 W cm-2 ) do not exhibit pronounced oxidation or temporal stress variation. These results serve as the basis for developing amorphous silicon carbide based dielectric encapsulation for implantable medical devices. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1654-1661, 2019.

Three-Dimensional Microcavity Array Electrodes for High-Capacitance All-Solid-State Flexible Microsupercapacitors.

We report novel three-dimensional (3D) microcavity array electrodes for high-capacitance all-solid-state microsupercapactiors. The microcavity arrays are formed in a polymer substrate via a plasma-assisted reactive ion etching (RIE) process and provide extra sidewall surface areas on which the active materials are grown in the form of nanofibers. This 3D structure leads to an increase in the areal capacitance by a factor of 2.56 for a 15-µm-deep cavity etching, agreeing well with the prediction. The fabricated microsupercapactiors exhibit a maximum areal capacitance of 65.1 mF cm(-2) (a volumetric capacitance of 93.0 F cm(-3)) and an energy density of 0.011 mWh cm(-2) (a volumetric energy density of 16.4 mWh cm(-3)) which substantially surpass previously reported values for all-solid-state flexible microsupercapacitors. The devices show good electrochemical stability under extended voltammetry cycles and bending cycles. It is demonstrated that they can sustain a radio frequency (rf) microsystem in a temporary absence of a power supply. These results suggest the potential utility of our 3D microsupercapactiors as miniaturized power sources in wearable and implantable medical devices.

Eyeglasses-powered, contact lens-like platform with high power transfer efficiency.

We present a contact lens-like platform that is wirelessly powered by an external coil embedded in eyeglasses via magnetic resonance coupling at 13.56 MHz. The platform is composed of a transparent parylene film as a host substrate, an embedded spiral inductor as a power receiving coil, and metal interconnects for additional electronics. A multilayer thin-film parylene packaging process is used to meet the form factor of a contact lens. A 36 µm-thick metal plating technique is employed on a parylene film to enhance the quality factor (Q) of the receiving coil (Q = 27.3 at 13.56 MHz). The power transfer method and techniques to compensate for coil misalignment are demonstrated on a pig eye, achieving a power transfer efficiency of 17.5 % at a 20-mm powering distance. The effect of tissue on the coil and the power transfer efficiency is examined. The high power transfer efficiency along with the wearable prototype demonstrated herein make promising progress toward smart contact lens in ocular diagnostics.

Wafer-scale integrated micro-supercapacitors on an ultrathin and highly flexible biomedical platform.

We present wafer-scale integrated micro-supercapacitors on an ultrathin and highly flexible parylene platform, as progress toward sustainably powering biomedical microsystems suitable for implantable and wearable applications. All-solid-state, low-profile (<30 µm), and high-density (up to ~500 µF/mm(2)) micro-supercapacitors are formed on an ultrathin (~20 µm) freestanding parylene film by a wafer-scale parylene packaging process in combination with a polyaniline (PANI) nanowire growth technique assisted by surface plasma treatment. These micro-supercapacitors are highly flexible and shown to be resilient toward flexural stress. Further, direct integration of micro-supercapacitors into a radio frequency (RF) rectifying circuit is achieved on a single parylene platform, yielding a complete RF energy harvesting microsystem. The system discharging rate is shown to improve by ~17 times in the presence of the integrated micro-supercapacitors. This result suggests that the integrated micro-supercapacitor technology described herein is a promising strategy for sustainably powering biomedical microsystems dedicated to implantable and wearable applications.