Nanoscale Phase and Orientation Mapping in Multiphase Polycrystalline Hafnium Zirconium Oxide Thin Films Using 4D-STEM and Automated Diffraction Indexing.

Ferroelectric hafnium zirconium oxide (HZO) holds promise for nextgeneration memory and transistors due to its superior scalability and seamless integration with complementary metal-oxide-semiconductor processing. A major challenge in developing this emerging ferroelectric material is the metastable nature of the non-centrosymmetric polar phase responsible for ferroelectricity, resulting in a coexistence of both polar and non-polar phases with uneven grain sizes and random orientations. Due to the structural similarity between the multiple phases and the nanoscale dimensions of the thin film devices, accurate measurement of phase-specific information remains challenging. Here, the application of 4D scanning transmission electron microscopy is demonstrated with automated electron diffraction pattern indexing to analyze multiphase polycrystalline HZO thin films, enabling the characterization of crystallographic phase and orientation across large working areas on the order of hundreds of nanometers. This approach offers a powerful characterization framework to produce a quantitative and statistically robust analysis of the intricate structure of HZO films by uncovering phase composition, polarization axis alignment, and unique phase distribution within the HZO film. This study introduces a novel approach for analyzing ferroelectric HZO, facilitating reliable characterization of process-structure-property relationships imperative to accelerating the growth optimization, performance, and successful implementation of ferroelectric HZO in devices.

3D printing of hollow geometries using blocking liquid substitution stereolithography.

Micrometer scale arbitrary hollow geometries within a solid are needed for a variety of applications including microfluidics, thermal management and metamaterials. A major challenge to 3D printing hollow geometries using stereolithography is the ability to retain empty spaces in between the solidified regions. In order to prevent unwanted polymerization of the trapped resin in the hollow spaces-known as print-through-significant constraints are generally imposed on the primary process parameters such as resin formulation, exposure conditions and layer thickness. Here, we report on a stereolithography process which substitutes the trapped resin with a UV blocking liquid to mitigate print-through. We investigate the mechanism of the developed process and determine guidelines for the formulation of the blocking liquid. The reported method decouples the relationship between the primary process parameters and their effect on print-through. Without having to optimize the primary process parameters to reduce print-through, hollow heights that exceed the limits of conventional stereolithography can be realized. We demonstrate fabrication of a variety of complex hollow geometries with cross-sectional features ranging from tens of micrometer to hundreds of micrometers in size. With the framework presented, this method may be employed for 3D printing functional hollow geometries for a variety of applications, and with improved freedom over the printing process (e.g. material choices, speed and resulting properties of the printed parts).

Microfluidic Paper-Based Analytical Device for Histidine Determination.

A laminated paper-based analytical device (LPAD) for histidine detection was fabricated from a chromatography filtration paper and laminate films. Histidine recognition was effected by histidyl-tRNA synthetase (HisRS), and its detection was signaled colorimetrically based on the molybdenum blue reaction. The analytical conditions and detectable concentration range of histidine were examined. The method provided selective quantification from 1 to 100 µM histidine. LPAD fabrication is considerably simple, involving only the craft-cutting of the chromatography filtration paper and laminate film, and is cost-effective.

Data retention and low voltage operation of Al2O3/Hf0.5Zr0.5O2 based ferroelectric tunnel junctions.

Ferroelectric random-access memories based on conventional perovskite materials are non-volatile but suffer from lack of CMOS compatibility, scalability limitation, and a destructive reading scheme. On the other hand, ferroelectric tunnel junctions based on CMOS compatible hafnium oxide are a promising candidate for future non-volatile memory technology due to their simple structure, scalability, low power consumption, high operation speed, and non-destructive read-out operation. Herein, we report an efficient strategy based on the interface-engineering approach to improve upon the tunneling electroresistance effect and data retention by depositing bilayer oxide heterostructure (Al2O3/Hf0.5Zr0.5O2) using atomic layer deposition (ALD) on Ge substrate which is treated in-situ ALD chamber with H2-plasma before film deposition. Integrating a thin ferroelectric layer i.e. Hf0.5Zr0.5O2 (8.4 nm) with a thin interface layer i.e. Al2O3 (1 nm) allowed us to reduce the operation (read and write) voltage to 1.4 V, and 4.3 V, respectively, while maintaining a good tunneling electroresistance or ON/OFF ratio above 10. Furthermore, an extrapolation to 1000 years at room temperature gives a residual ON/OFF ratio of 4.

Electrode impedance analysis of chronic tungsten microwire neural implants: understanding abiotic vs. biotic contributions.

Changes in biotic and abiotic factors can be reflected in the complex impedance spectrum of the microelectrodes chronically implanted into the neural tissue. The recording surface of the tungsten electrode in vivo undergoes abiotic changes due to recording site corrosion and insulation delamination as well as biotic changes due to tissue encapsulation as a result of the foreign body immune response. We reported earlier that large changes in electrode impedance measured at 1 kHz were correlated with poor electrode functional performance, quantified through electrophysiological recordings during the chronic lifetime of the electrode. There is a need to identity the factors that contribute to the chronic impedance variation. In this work, we use numerical simulation and regression to equivalent circuit models to evaluate both the abiotic and biotic contributions to the impedance response over chronic implant duration. COMSOL® simulation of abiotic electrode morphology changes provide a possible explanation for the decrease in the electrode impedance at long implant duration while biotic changes play an important role in the large increase in impedance observed initially.

Abiotic-biotic characterization of Pt/Ir microelectrode arrays in chronic implants.

Pt/Ir electrodes have been extensively used in neurophysiology research in recent years as they provide a more inert recording surface as compared to tungsten or stainless steel. While floating microelectrode arrays (FMA) consisting of Pt/Ir electrodes are an option for neuroprosthetic applications, long-term in vivo functional performance characterization of these FMAs is lacking. In this study, we have performed comprehensive abiotic-biotic characterization of Pt/Ir arrays in 12 rats with implant periods ranging from 1 week up to 6 months. Each of the FMAs consisted of 16-channel, 1.5 mm long, and 75 µm diameter microwires with tapered tips that were implanted into the somatosensory cortex. Abiotic characterization included (1) pre-implant and post-explant scanning electron microscopy (SEM) to study recording site changes, insulation delamination and cracking, and (2) chronic in vivo electrode impedance spectroscopy. Biotic characterization included study of microglial responses using a panel of antibodies, such as Iba1, ED1, and anti-ferritin, the latter being indicative of blood-brain barrier (BBB) disruption. Significant structural variation was observed pre-implantation among the arrays in the form of irregular insulation, cracks in insulation/recording surface, and insulation delamination. We observed delamination and cracking of insulation in almost all electrodes post-implantation. These changes altered the electrochemical surface area of the electrodes and resulted in declining impedance over the long-term due to formation of electrical leakage pathways. In general, the decline in impedance corresponded with poor electrode functional performance, which was quantified via electrode yield. Our abiotic results suggest that manufacturing variability and insulation material as an important factor contributing to electrode failure. Biotic results show that electrode performance was not correlated with microglial activation (neuroinflammation) as we were able to observe poor performance in the absence of neuroinflammation, as well as good performance in the presence of neuroinflammation. One biotic change that correlated well with poor electrode performance was intraparenchymal bleeding, which was evident macroscopically in some rats and presented microscopically by intense ferritin immunoreactivity in microglia/macrophages. Thus, we currently consider intraparenchymal bleeding, suboptimal electrode fabrication, and insulation delamination as the major factors contributing toward electrode failure.

The use of polyurethane as an elastomer in thermoplastic microfluidic devices and the study of its creep properties.

We report using polyurethane (PU) as an elastomer in microvalves integrated with thermoplastic microfluidic devices. Elastomer-based microvalves have been used in a number of applications and the elastomer often used is PDMS. Although it is a convenient material for prototyping, PDMS has been recognized to possess shortcomings such as solvent incompatibility and unfavorable manufacturability. We investigated the use of PU as an elastomer to address the challenges. A reliable method was developed to bond hybrid materials such as PU and cyclic olefin copolymer. The film thickness from 3.5 to 24.5 µm was studied to identify an appropriate thickness of PU films for desirable elasticity in microvalves. We integrated PU with thermally actuated, elastomer-based microvalves in thermoplastic devices. Valve actuations were demonstrated, and the relationship between the valve actuation time and heater power was studied. We compared PU with PDMS in terms of their microvalve performance. Valves with PDMS failed to function after two weeks since the thermal-sensitive solution evaporated through porous PDMS membrane, whereas the same valve with PU functioned properly after eight months. In addition, we evaluated the creep and creep recovery of PU, which is a common phenomenon of viscoelastic materials and is related to the long-term elastic property of PU after prolonged use.

A highly compliant serpentine shaped polyimide interconnect for front-end strain relief in chronic neural implants.

While the signal quality of recording neural electrodes is observed to degrade over time, the degradation mechanisms are complex and less easily observable. Recording microelectrodes failures are attributed to different biological factors such as tissue encapsulation, immune response, and disruption of blood-brain barrier (BBB) and non-biological factors such as strain due to micromotion, insulation delamination, corrosion, and surface roughness on the recording site (1-4). Strain due to brain micromotion is considered to be one of the important abiotic factors contributing to the failure of the neural implants. To reduce the forces exerted by the electrode on the brain, a high compliance 2D serpentine shaped electrode cable was designed, simulated, and measured using polyimide as the substrate material. Serpentine electrode cables were fabricated using MEMS microfabrication techniques, and the prototypes were subjected to load tests to experimentally measure the compliance. The compliance of the serpentine cable was numerically modeled and quantitatively measured to be up to 10 times higher than the compliance of a straight cable of same dimensions and material.

Comprehensive characterization and failure modes of tungsten microwire arrays in chronic neural implants.

For nearly 55 years, tungsten microwires have been widely used in neurophysiological experiments in animal models to chronically record neuronal activity. While tungsten microwires initially provide stable recordings, their inability to reliably record high-quality neural signals for tens of years has limited their efficacy for neuroprosthetic applications in humans. Comprehensive understanding of the mechanisms of electrode performance and failure is necessary for developing next generation neural interfaces for humans. In this study, we evaluated the abiotic (electrophysiology, impedance, electrode morphology) and biotic (microglial reactivity, blood-brain barrier disruption, biochemical markers of axonal injury) effects of 16-channel, 50 µm diameter, polyimide insulated tungsten microwires array for implant durations that ranged from acute to up to 9 months in 25 rats. Daily electrode impedance spectroscopy, electrophysiological recordings, blood and cerebrospinal fluid (CSF) withdrawals, and histopathological analysis were performed to study the time-varying effects of chronic electrode implantation. Structural changes at the electrode recording site were observed as early as within 2-3 h of electrode insertion. Abiotic analysis indicated the first 2-3 weeks following surgery was the most dynamic period in the chronic electrode lifetime as there were greater variations in the electrode impedance, functional electrode performance, and the structural changes occurring at the electrode recording tips. Electrode recording site deterioration continued for the long-term chronic animals as insulation damage occurred and recording surface became more recessed over time. In general, electrode impedance and functional performance had smaller daily variations combined with reduced electrode recording site changes during the chronic phase. Histopathological studies were focused largely on characterizing microglial cell responses to electrode implantation. We found that activated microglia were present near the electrode tracks in all non-acute animals studied, thus indicating presence of a neuroinflammatory response regardless of post-implantation survival times and electrode performance. Conversely, dystrophic microglia detectable as fragmented cells were found almost exclusively in acute animals surviving only few hours after implantation. While there was no consistent relationship between microglial cell responses and electrode performance, we noticed co-occurrence of high ferritin expression, intraparenchymal bleeding, and microglial degeneration suggesting presence of excessive oxidative stress via Fenton chemistry. Biochemical analysis indicated that these electrodes always caused a persistent release of axonal injury biomarkers even several months after implantation suggesting persistent tissue damage. Our study suggests that mechanisms of electrode failure are multi-factorial involving both abiotic and biotic parameters. Since these failure modes occur concurrently and cannot be isolated from one another, the lack of consistent relationship between electrode performance and microglial responses in our results suggest that one or more of the abiotic factors were equally responsible for degradation in electrode performance over long periods of time.

Electrode failure: tissue, electrical, and material responses.

The development of invasive, rehabilitative neuroprosthetics for humans requires reliable neural probes that are capable of recording large ensembles of neurons for a long period of time. Recent advances in the development of neuroprosthetics in animals and humans have shown that communication and control can be directly derived from the central nervous system (CNS) for restoring lost motor ability. This proof of concept has opened the possibility of new therapies for the millions of individuals suffering from neurological disorders of the nervous system. The success of these therapies hinges on the ability to reliably access the relevant signals from the brain with high quality for the lifetime of the patient. As a result, research has focused on the cascade of events that follow chronic implantation of microelectrodes and temporal degradation in the signal and electrode quality: signal-to-noise ratio, noise floor, peak amplitude, and neuronal yield. Implanted microelectrodes have been reported to suffer from time-dependent degradation in signal quality due to unknown issues related to tissue interfaces.

Comprehensive characterization of tungsten microwires in chronic neurocortical implants.

The long-term performance of chronic microelectrode array implants for neural ensemble recording is affected by temporal degradation in signal quality due to several factors including structural changes in the recording surface, electrical responses, and tissue immune reactivity. This study combines the information available from the temporal aggregation of both biotic and abiotic metrics to analyze and quantify the combined effects on long-term performance. Study of a 42-day implant showed there was a functional relationship between the measured impedance and the array neuronal yield. This was correlated with structural changes in the recording sites, microglial activation/degeneration, and elevation of a blood biochemical marker for axonal injury. We seek to elucidate the mechanisms of chronic microelectrode array failure through the study of the combined effects of these biotic and abiotic factors.

Corrosion of tungsten microelectrodes used in neural recording applications.

In neuroprosthetic applications, long-term electrode viability is necessary for robust recording of the activity of neural populations used for generating communication and control signals. The corrosion of tungsten microwire electrodes used for intracortical recording applications was analyzed in a controlled bench-top study and compared to the corrosion of tungsten microwires used in an in vivo study. Two electrolytes were investigated for the bench-top electrochemical analysis: 0.9% phosphate buffered saline (PBS) and 0.9% PBS containing 30 mM of hydrogen peroxide. The oxidation and reduction reactions responsible for corrosion were found by measurement of the open circuit potential and analysis of Pourbaix diagrams. Dissolution of tungsten to form the tungstic ion was found to be the corrosion mechanism. The corrosion rate was estimated from the polarization resistance, which was extrapolated from the electrochemical impedance spectroscopy data. The results show that tungsten microwires in an electrolyte of PBS have a corrosion rate of 300-700 µm/yr. The corrosion rate for tungsten microwires in an electrolyte containing PBS and 30 mM H2O2 is accelerated to 10,000-20,000 µm/yr. The corrosion rate was found to be controlled by the concentration of the reacting species in the cathodic reaction (e.g. O2 and H2O2). The in vivo corrosion rate, averaged over the duration of implantation, was estimated to be 100 µm/yr. The reduced in vivo corrosion rate as compared to the bench-top rate is attributed to decreased rate of oxygen diffusion caused by the presence of a biological film and a reduced concentration of available oxygen in the brain.

Chemical-assisted bonding of thermoplastics/elastomer for fabricating microfluidic valves.

Thermoplastics such as cyclic olefin copolymer (COC) and polymethylmethacrylate (PMMA) have been increasingly used in fabricating microfluidic devices. However, the state-of-the-art microvalve technology is a polydimethylsiloxane (PDMS)-based three-layer structure. In order to integrate such a valve with a thermoplastics-based microfluidic device, a bonding method for thermoplastics/PDMS must be developed. We report here a method to bond COC with PDMS through surface activation by corona discharge, surface modification using 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), and thermal annealing. The method is also applicable to PMMA. The bonding strength between thermoplastics and PDMS was represented by the peeling force, which was measured using a method established by the International Organization for Standardization (ISO). The bonding strength measurement offered an objective and quantitative indicator for protocol optimization, as well as comparison with other PDMS-associated bonding methods. Using optimized bonding conditions, two valve arrays were fabricated in a COC/PDMS/COC device and cyclic operations of valve closing/opening were successfully demonstrated. The valve-containing devices withstood 100 psi (∼689 KPa) without delamination. Further, we integrated such valve arrays in a device for protein separation and demonstrated isoelectric focusing in the presence of valves.

Coupling biotic and abiotic metrics to create a testbed for predicting neural electrode performance.

In this work, we develop an experimental testbed that couples biotic and abiotic metrics for studying, quantifying and predicting the effects of chronic electrode implantation on neural electrode performance. The rationale is based on the observation that long-term functionality is the outcome of the interactions between the dynamics of the neuronal environment and the properties of the electrode itself. By combining and analyzing the substantially richer information available in the spatiotemporal dynamics of neurons with biotic and abiotic metrics such as biochemical markers, histochemistry, SEM imaging, and electrochemistry, we seek to quantitatively improve our understanding of the functional modifications underlying the long-term responses of electrode implants. The goal is to ultimately enable the design of future reliable interfaces. In our preliminary analysis using this biotic-abiotic approach of an electrode 18 days post-implant, we observed both structural and histochemical responses related to chronic electrode implantation. These were coupled to daily functional changes in electrode performance. Interestingly, these changes were not correlated with markers of brain injury at the time of electrode explantation. Future work using this multidisciplinary approach is directed to providing a detailed perspective into long-term microelectrode performance.

An implantable integrated low-power amplifier-microelectrode array for Brain-Machine Interfaces.

One of the important challenges in designing Brain-Machine Interfaces (BMI) is to build implantable systems that have the ability to reliably process the activity of large ensembles of cortical neurons. In this paper, we report the design, fabrication, and testing of a polyimide-based microelectrode array integrated with a low-power amplifier as part of the Florida Wireless Integrated Recording Electrode (FWIRE) project at the University of Florida developing a fully implantable neural recording system for BMI applications. The electrode array was fabricated using planar micromachining MEMS processes and hybrid packaged with the amplifier die using a flip-chip bonding technique. The system was tested both on bench and in-vivo. Acute and chronic neural recordings were obtained from a rodent for a period of 42 days. The electrode-amplifier performance was analyzed over the chronic recording period with the observation of a noise floor of 4.5 microVrms, and an average signal-to-noise ratio of 3.8.

Manufacturable plastic microfluidic valves using thermal actuation.

A low-cost, manufacturable, thermally actuated, plastic microfluidic valve has been developed. The valve contains an encapsulated, temperature-sensitive fluid, which expands, deflecting a thin elastomeric film into a fluidic channel to control fluid flow. The power input for thermal expansion of each microfluidic valve can be controlled using a printed circuit board (PCB)-based controller, which is suitable for mass production and large-scale integration. A plastic microfluidic device with such valves was fabricated using compression molding and thermal lamination. The operation of the valves was investigated by measuring a change in the microchannel's ionic conduction current mediated by the resistance variation corresponding to the deflection of the microvalve. Valve closing was also confirmed by the disappearance of fluorescence when a fluorescent solution was displaced in the valve region. Valve operation was characterized for heater power ranging from 36 mW to 80 mW. When the valve was actuating, the local channel temperature was 10 to 19 degrees C above the ambient temperature depending on the heater power used. Repetitive valve operations (up to 50 times) have been demonstrated with a flow resulting from a hydrostatic head. Valve operation was tested for a flow rate of 0.33-4.7 microL/min.

Demonstration of a wireless, self-powered, electroacoustic liner system.

This paper demonstrates the system operation of a self-powered active liner for the suppression of aircraft engine noise. The fundamental element of the active liner system is an electromechanical Helmholtz resonator (EMHR), which consists of a Helmholtz resonator with one of its rigid walls replaced with a circular piezoceramic composite plate. For this system demonstration, two EMHR elements are used, one for acoustic impedance tuning and one for energy harvesting. The EMHR used for acoustic impedance tuning is shunted with a variable resistive load, while the EMHR used for energy harvesting is shunted to a flyback power converter and storage element. The desired acoustic impedance conditions are determined externally, and wirelessly transmitted to the liner system. The power for the receiver and the impedance tuning circuitry in the liner are supplied by the harvested energy. Tuning of the active liner is demonstrated at three different sound pressure levels (148, 151, and 153 dB) in order to show the robustness of the energy harvesting and storage system. An acoustic tuning range of approximately 200 Hz is demonstrated for each of the three available power levels.

Acoustic energy harvesting using an electromechanical Helmholtz resonator.

This paper presents the development of an acoustic energy harvester using an electromechanical Helmholtz resonator (EMHR). The EMHR consists of an orifice, cavity, and a piezoelectric diaphragm. Acoustic energy is converted to mechanical energy when sound incident on the orifice generates an oscillatory pressure in the cavity, which in turns causes the vibration of the diaphragm. The conversion of acoustic energy to electrical energy is achieved via piezoelectric transduction in the diaphragm of the EMHR. Moreover, the diaphragm is coupled with energy reclamation circuitry to increase the efficiency of the energy conversion. Lumped element modeling of the EMHR is used to provide physical insight into the coupled energy domain dynamics governing the energy reclamation process. The feasibility of acoustic energy reclamation using an EMHR is demonstrated in a plane wave tube for two power converter topologies. The first is comprised of only a rectifier, and the second uses a rectifier connected to a flyback converter to improve load matching. Experimental results indicate that approximately 30 mW of output power is harvested for an incident sound pressure level of 160 dB with a flyback converter. Such power level is sufficient to power a variety of low power electronic devices.

Flexible polymer substrate and tungsten microelectrode array for an implantable neural recording system.

This paper describes the process flow and testing of a substrate for a fully implantable neural recording system. Tungsten microwires are hybrid-packaged on a micromachined flexible polymer substrate forming an intracortical microelectrode array for brain machine interfaces. The microelectrode array is characterized on the bench top and tested in vivo. The microelectrode noise floor is less than 2 microV and acute recording results show a signal to noise ratio of 9.9-17.3 dB. The technique of hybrid fabrication of the electrodes on a flexible substrate provides a general platform for the development of an implantable neural recording system.