Dustin Simon

Thiol-ene/acrylate substrates for softening intracortical electrodes

Neural interfaces have traditionally been fabricated on rigid and planar substrates, including silicon and engineering thermoplastics. However, the neural tissue with which these devices interact is both 3D and highly compliant. The mechanical mismatch at the biotic-abiotic interface is expected to contribute to the tissue response that limits chronic signal recording and stimulation. In this work, novel ternary thiol-ene/acrylate polymer networks are used to create softening substrates for neural recording electrodes. Thermomechanical properties of the substrates are studied through differential scanning calorimetry and dynamic mechanical analysis both before and after exposure physiological conditions. This substrate system softens from more than 1 GPa to 18 MPa on exposure to physiological conditions: reaching body temperature and taking up less than 3% fluid. The impedance of 177 µm(2) gold electrodes electroplated with platinum black fabricated on these substrates is measured to be 206 kΩ at 1 kHz. Specifically, intracortical electrodes are fabricated, implanted, and used to record driven neural activity. This work describes the first substrate system that can use the full capabilities of photolithography, respond to physiological conditions by softening markedly after insertion, and record driven neural activity for 4 weeks.

Smart Polymers for Neural Interfaces

Thermomechanical properties of smart polymers can be specifically tuned to address critical problems in neural interfaces. A compilation of materials and approaches is presented from each of three often overlapping research communities: shape memory polymers, hydrogels, and neural interfaces. The path toward chronically implantable devices for neural recording and stimulation relies on careful control of mechanical, chemical, electronic and geometric properties of next generation devices. These phenomena are described and put into a context of modulus changing materials, as opposed to the current focus on shape changing materials, as a paradigm that may lead to new discoveries addressing unmet clinical needs.

Mechanical Cycling Stability of Organic Thin Film Transistors on Shape Memory Polymers

Organic thin film transistors on shape memory polymers are fabricated by full photolithography. Devices show high mobility (0.2 cm(2) V(-1) s(-1)) and close to zero threshold voltage (-4.5 V) when characterized as fabricated. After 1, 10, and 100 deformation cycles and in a deformed, metastable shape memory transition state, changes in mobility and V(th) are measured and indicate sustained device functionality.

Design and demonstration of an intracortical probe technology with tunable modulus.

Intracortical probe technology, consisting of arrays of microelectrodes, offers a means of recording the bioelectrical activity from neural tissue. A major limitation of existing intracortical probe technology pertains to limited lifetime of 6 months to a year of recording after implantation. A major contributor to device failure is widely believed to be the interfacial mechanical mismatch of conventional stiff intracortical devices and the surrounding brain tissue. We describe the design, development, and demonstration of a novel functional intracortical probe technology that has a tunable Youngs modulus from ∼2 GPa to ∼50 MPa. This technology leverages advances in dynamically softening materials, specifically thiol-ene/acrylate thermoset polymers, which exhibit minimal swelling of < 3% weight upon softening in vitro. We demonstrate that a shape memory polymer-based multichannel intracortical probe can be fabricated, that the mechanical properties are stable for at least 2 months and that the device is capable of single unit recordings for durations up to 77 days in vivo. This novel technology, which is amenable to processes suitable for manufacturing via standard semiconductor fabrication techniques, offers the capability of softening in vivo to reduce the tissue-device modulus mismatch to ultimately improve long term viability of neural recordings.

Integration of High-Charge-Injection-Capacity Electrodes onto Polymer Softening Neural Interfaces

Softening neural interfaces are implanted stiff to enable precise insertion, and they soften in physiological conditions to minimize modulus mismatch with tissue. In this work, a high-charge-injection-capacity iridium electrode fabrication process is detailed. For the first time, this process enables integration of iridium electrodes onto softening substrates using photolithography to define all features in the device. Importantly, no electroplated layers are utilized, leading to a highly scalable method for consistent device fabrication. The iridium electrode is metallically bonded to the gold conductor layer, which is covalently bonded to the softening substrate via sulfur-based click chemistry. The resulting shape-memory polymer neural interfaces can deliver more than 2 billion symmetric biphasic pulses (100 μs/phase), with a charge of 200 μC/cm(2) and geometric surface area (GSA) of 300 μm(2). A transfer-by-polymerization method is used in combination with standard semiconductor processing techniques to fabricate functional neural probes onto a thiol-ene-based, thin film substrate. Electrical stability is tested under simulated physiological conditions in an accelerated electrical aging paradigm with periodic measurement of electrochemical impedance spectra (EIS) and charge storage capacity (CSC) at various intervals. Electrochemical characterization and both optical and scanning electron microscopy suggest significant breakdown of the 600 nm-thick parylene-C insulation, although no delamination of the conductors or of the final electrode interface was observed. Minor cracking at the edges of the thin film iridium electrodes was occasionally observed. The resulting devices will provide electrical recording and stimulation of the nervous system to better understand neural wiring and timing, to target treatments for debilitating diseases, and to give neuroscientists spatially selective and specific tools to interact with the body. This approach has uses for cochlear implants, nerve cuff electrodes, penetrating cortical probes, spinal stimulators, blanket electrodes for the gut, stomach, and visceral organs and a host of other custom nerve-interfacing devices.

Degradable, silyl ether thiol–ene networks

A system of multifunctional silyl ether containing alkene and thiol monomers are synthesized and polymerized into uniform degradable networks with widely tunable thermomechanical properties. The glass transition temperature of the hydrolytically unstable networks can be controlled between −60 °C and 40 °C. Near total degradation is observed and the rate of degradation is controlled to occur between hours and months. Dynamic mechanical analysis, mass loss, uniaxial compression testing, multinuclear NMR spectroscopy, and gas chromatography-mass spectrometry are utilized to characterize the degradation of these networks. Importantly, this system of materials allows for rapid hydrolytic degradation that is not preceded by swelling. These degradable polymers are demonstrated to be compatible with microfabrication techniques, namely photolithography. As a demonstration, partially biodegradable cortical electrodes were fabricated and electrochemically characterized on silyl ether substrates.

Hydrolytically Stable Thiol–ene Networks for Flexible Bioelectronics

Hydrolytically stable, tunable modulus polymer networks are demonstrated to survive harsh alkaline environments and offer promise for use in long-term implantable bioelectronic medicines known as electroceuticals. Todays polymer networks (such as polyimides or polysiloxanes) succeed in providing either stiff or soft substrates for bioelectronics devices; however, the capability to significantly tune the modulus of such materials is lacking. Within the space of materials with easily modified elastic moduli, thiol-ene copolymers are a subset of materials that offer a promising solution to build next generation flexible bioelectronics but have typically been susceptible to hydrolytic degradation chronically. In this inquiry, we demonstrate a materials space capable of tuning the substrate modulus and explore the mechanical behavior of such networks. Furthermore, we fabricate an array of microelectrodes that can withstand accelerated aging environments shown to destroy conventional flexible bioelectronics.