Chronic stability of activated iridium oxide film voltage transients from wireless floating microelectrode arrays.

Successful monitoring of the condition of stimulation electrodes is critical for maintaining chronic device performance for neural stimulation. As part of pre-clinical safety testing in preparation for a visual prostheses clinical trial, we evaluated the stability of the implantable devices and stimulation electrodes using a combination of current pulsing in saline and in canine visual cortex. Specifically, in saline we monitored the stability and performance of 3000 µm2 geometric surface area activated iridium oxide film (AIROF) electrodes within a wireless floating microelectrode array (WFMA) by measuring the voltage transient (VT) response through reverse telemetry. Eight WFMAs were assessed in vitro for 24 days, where n = 4 were pulsed continuously at 80 µA (16 nC/phase) and n = 4 remained in solution with no applied stimulation. Subsequently, twelve different WFMAs were implanted in visual cortex in n = 3 canine subjects (4 WFMAs each). After a 2-week recovery period, half of the electrodes in each of the twelve devices were pulsed continuously for 24 h at either 20, 40, 63, or 80 µA (200 µs pulse width, 100 Hz). VTs were recorded to track changes in the electrodes at set time intervals in both the saline and in vivo study. The VT response of AIROF electrodes remained stable during pulsing in saline over 24 days. Electrode polarization and driving voltage changed by less than 200 mV on average. The AIROF electrodes also maintained consistent performance, overall, during 24 h of pulsing in vivo. Four of the in vivo WFMA devices showed a change in polarization, access voltage, or driving voltage over time. However, no VT recordings indicated electrode failure, and the same trend was typically seen in both pulsed and unpulsed electrodes within the same device. Overall, accelerated stimulation testing in saline and in vivo indicated that AIROF electrodes in the WFMA were able to consistently deliver up to 16 nC per pulse and would be suitable for chronic clinical use.

Charge injection characteristics of sputtered ruthenium oxide electrodes for neural stimulation and recording.

We have studied the charge-injection characteristics and electrochemical impedance of sputtered ruthenium oxide (RuOx ) films as electrode coatings for neural stimulation and recording electrodes. RuOx films were deposited by reactive DC magnetron sputtering, using a combination of water vapor and oxygen gas as reactive plasma constituents. The cathodal charge storage capacity of planar RuOx electrodes was found to be 54.6 ± 9.5 mC/cm2 (mean ± SD, n = 12), and the charge-injection capacity in a 0.2-ms cathodal current pulse was found to be 7.1 ± 0.3 mC/cm2 (mean ± SD, n = 15) at 0.6 V positive bias versus Ag|AgCl, in phosphate buffer saline at room temperature for ~250 nm thick films. In general, the RuOx films exhibited high charge-injection capacities, with or without a positive interpulse bias, comparable to sputtered iridium oxide (SIROF) coatings. The charge-injection capacity increased monotonically with film thickness from 120 to 630 nm, and reached 11.30 ± 0.34 mC/cm2 (mean ± SD, n = 5) at 0.6 V bias versus Ag|AgCl at 630 nm film thickness. In addition, RuOx films showed minimal changes in electrochemical characteristics over 1.5 billion cycles of constant current pulsing at a charge density of 408 µC/cm2 (8 nC/phase, 200 µs pulse width). The findings of low-impedance, high charge-injection capacity, and long-term pulsing stability suggest the suitability of RuOx as a comparatively inexpensive and favorable choice of electrode material for neural stimulation and recording.

In Vitro Electrochemical Properties of Titanium Nitride Neural Stimulating and Recording Electrodes as a Function of Film Thickness and Voltage Biasing.

Thin film titanium nitride (TiN), with a geometric surface area of 2,000 µm2, was deposited on planar test structures with thicknesses of 95, 185, 315, and 645 nm. Electrochemical measurements of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and voltage transient (VT) were performed. We found that impedance values decreased and charge storage and charge injection capacities increased with increasing film thicknesses. Additionally, applying a anodic bias to TiN can increase the charge injection of the film to nearly double that of a non-biased film.

Sputtered Ruthenium Oxide Neural Stimulation Electrodes.

We have investigated the charge-injection properties of sputtered ruthenium oxide (RuOx) coatings deposited on planar microelectrode arrays. Substantial charge was found to be available for injection within -0.6/0.6 V vs Ag|AgCl potential limits for the sputtered RuOx film. The charge-injection capacity increased further upon extending the potential limits to -0.7/0.7 V vs Ag|AgCl. No oxygen reduction, an unwanted side reaction, was observed during the pulsing of sputtered RuOx microelectrodes in phosphate buffered saline solution. Additionally, the RuOx coatings were found to be electrochemically stable for up to 1-billion-cycles of constant current stimulation pulsing at 8 nC/phase in model-ISF at 37° C.

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.

Activated iridium oxide film (AIROF) electrodes for neural tissue stimulation.

OBJECTIVE: Iridium oxide films are commonly used as a high charge-injection electrode material in neural devices. Yet, few studies have performed in-depth assessments of material performance versus film thickness, especially for films grown on three-dimensional (instead of planar) metal surfaces in neutral pH electrolyte solutions. Further, few studies have investigated the driving voltage requirements for constant-current stimulation using activated iridium oxide (AIROF) electrodes, which will be a key constraint for future use in wirelessly powered neural devices. APPROACH: In this study, iridium microwire probes were activated by repeated potential pulsing in room temperature phosphate buffered saline (pH 7.1-7.3). Electrochemical measurements were recorded in three different electrolyte conditions for probes with different geometric surface areas (GSAs) as the AIROF thickness was increased. MAIN RESULTS: Maintaining an anodic potential bias during the inter-pulse interval was required for AIROF electrodes to deliver charge levels considered necessary for neural stimulation. Potential pulsing for 100-200 cycles was sufficient to achieve charge injection levels of 2.5 mC cm-2 (50 nC/phase in a biphasic pulse) in PBS with 2000 µm2 iridium probes. Increasing the electrode surface area to 3000 µm2 and 4000 µm2 significantly increased charge-injection capacity, reduced the driving voltage required to deliver a fixed amount of charge, and reduced polarization of the electrodes during constant-current pulsing. SIGNIFICANCE: This study establishes methods for choosing an activation protocol and a desired GSA for three-dimensional iridium electrodes suitable for neural tissue insertion and stimulation, and provides guidelines for evaluating electrochemical performance of AIROF using model saline solutions.

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.

Electrical Properties of Thiol-ene-based Shape Memory Polymers Intended for Flexible Electronics.

Thiol-ene/acrylate-based shape memory polymers (SMPs) with tunable mechanical and thermomechanical properties are promising substrate materials for flexible electronics applications. These UV-curable polymer compositions can easily be polymerized onto pre-fabricated electronic components and can be molded into desired geometries to provide a shape-changing behavior or a tunable softness. Alternatively, SMPs may be prepared as a flat substrate, and electronic circuitry may be built directly on top by thin film processing technologies. Whichever way the final structure is produced, the operation of electronic circuits will be influenced by the electrical and mechanical properties of the underlying (and sometimes also encapsulating) SMP substrate. Here, we present electronic properties, such as permittivity and resistivity of a typical SMP composition that has a low glass transition temperature (between 40 and 60 °C dependent on the curing process) in different thermomechanical states of polymer. We fabricated parallel plate capacitors from a previously reported SMP composition (fully softening (FS)-SMP) using two different curing processes, and then we determined the electrical properties of relative permittivity and resistivity below and above the glass transition temperature. Our data shows that the curing process influenced the electrical permittivity, but not the electrical resistivity. Corona-Kelvin metrology evaluated the quality of the surface of FS-SMP spun on the wafer. Overall, FS-SMP demonstrates resistivity appropriate for use as an insulating material.

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.

Amorphous Silicon Carbide Platform for Next Generation Penetrating Neural Interface Designs.

Microelectrode arrays that consistently and reliably record and stimulate neural activity under conditions of chronic implantation have so far eluded the neural interface community due to failures attributed to both biotic and abiotic mechanisms. Arrays with transverse dimensions of 10 µm or below are thought to minimize the inflammatory response; however, the reduction of implant thickness also decreases buckling thresholds for materials with low Young's modulus. While these issues have been overcome using stiffer, thicker materials as transport shuttles during implantation, the acute damage from the use of shuttles may generate many other biotic complications. Amorphous silicon carbide (a-SiC) provides excellent electrical insulation and a large Young's modulus, allowing the fabrication of ultrasmall arrays with increased resistance to buckling. Prototype a-SiC intracortical implants were fabricated containing 8 - 16 single shanks which had critical thicknesses of either 4 µm or 6 µm. The 6 µm thick a-SiC shanks could penetrate rat cortex without an insertion aid. Single unit recordings from SIROF-coated arrays implanted without any structural support are presented. This work demonstrates that a-SiC can provide an excellent mechanical platform for devices that penetrate cortical tissue while maintaining a critical thickness less than 10 µm.

Characterization of the Neuroinflammatory Response to Thiol-ene Shape Memory Polymer Coated Intracortical Microelectrodes.

Thiol-ene based shape memory polymers (SMPs) have been developed for use as intracortical microelectrode substrates. The unique chemistry provides precise control over the mechanical and thermal glass-transition properties. As a result, SMP substrates are stiff at room temperature, allowing for insertion into the brain without buckling and subsequently soften in response to body temperatures, reducing the mechanical mismatch between device and tissue. Since the surface chemistry of the materials can contribute significantly to the ultimate biocompatibility, as a first step in the characterization of our SMPs, we sought to isolate the biological response to the implanted material surface without regards to the softening mechanics. To accomplish this, we tightly controlled for bulk stiffness by comparing bare silicon 'dummy' devices to thickness-matched silicon devices dip-coated with SMP. The neuroinflammatory response was evaluated after devices were implanted in the rat cortex for 2 or 16 weeks. We observed no differences in the markers tested at either time point, except that astrocytic scarring was significantly reduced for the dip-coated implants at 16 weeks. The surface properties of non-softening thiol-ene SMP substrates appeared to be equally-tolerated and just as suitable as silicon for neural implant substrates for applications such as intracortical microelectrodes, laying the groundwork for future softer devices to improve upon the prototype device performance presented here.

Chronic Intracortical Recording and Electrochemical Stability of Thiol-ene/Acrylate Shape Memory Polymer Electrode Arrays.

Current intracortical probe technology is limited in clinical implementation due to the short functional lifetime of implanted devices. Devices often fail several months to years post-implantation, likely due to the chronic immune response characterized by glial scarring and neuronal dieback. It has been demonstrated that this neuroinflammatory response is influenced by the mechanical mismatch between stiff devices and the soft brain tissue, spurring interest in the use of softer polymer materials for probe encapsulation. Here, we demonstrate stable recordings and electrochemical properties obtained from fully encapsulated shape memory polymer (SMP) intracortical electrodes implanted in the rat motor cortex for 13 weeks. SMPs are a class of material that exhibit modulus changes when exposed to specific conditions. The formulation used in these devices softens by an order of magnitude after implantation compared to its dry, room-temperature modulus of ~2 GPa.

Thin Film Multi-Electrode Softening Cuffs for Selective Neuromodulation.

Silicone nerve cuff electrodes are commonly implanted on relatively large and accessible somatic nerves as peripheral neural interfaces. While these cuff electrodes are soft (1-50 MPa), their self-closing mechanism requires of thick walls (200-600 µm), which in turn contribute to fibrotic tissue growth around and inside the device, compromising the neural interface. We report the use of thiol-ene/acrylate shape memory polymer (SMP) for the fabrication of thin film multi-electrode softening cuffs (MSC). We fabricated multi-size MSC with eight titanium nitride (TiN) electrodes ranging from 1.35 to 13.95 × 10-4 cm2 (1-3 kΩ) and eight smaller gold (Au) electrodes (3.3 × 10-5 cm2; 750 kΩ), that soften at physiological conditions to a modulus of 550 MPa. While the SMP material is not as soft as silicone, the flexural forces of the SMP cuff are about 70-700 times lower in the MSC devices due to the 30 µm thick film compared to the 600 µm thick walls of the silicone cuffs. We demonstrated the efficacy of the MSC to record neural signals from rat sciatic and pelvic nerves (1000 µm and 200 µm diameter, respectively), and the selective fascicular stimulation by current steering. When implanted side-by-side and histologically compared 30 days thereafter, the MSC devices showed significantly less inflammation, indicated by a 70-80% reduction in ED1 positive macrophages, and 54-56% less fibrotic vimentin immunoreactivity. Together, the data supports the use of MSC as compliant and adaptable technology for the interfacing of somatic and autonomic peripheral nerves.

Chronic recording and electrochemical performance of Utah microelectrode arrays implanted in rat motor cortex.

Multisite implantable electrode arrays serve as a tool to understand cortical network connectivity and plasticity. Furthermore, they enable electrical stimulation to drive plasticity, study motor/sensory mapping, or provide network input for controlling brain-computer interfaces. Neurobehavioral rodent models are prevalent in studies of motor cortex injury and recovery as well as restoration of auditory/visual cues due to their relatively low cost and ease of training. Therefore, it is important to understand the chronic performance of relevant electrode arrays in rodent models. In this report, we evaluate the chronic recording and electrochemical performance of 16-channel Utah electrode arrays, the current state-of-the-art in pre-/clinical cortical recording and stimulation, in rat motor cortex over a period of 6 mo. The single-unit active electrode yield decreased from 52.8 ± 10.0 ( week 1) to 13.4 ± 5.1% ( week 24). Similarly, the total number of single units recorded on all electrodes across all arrays decreased from 106 to 15 over the same time period. Parallel measurements of electrochemical impedance spectra and cathodic charge storage capacity exhibited significant changes in electrochemical characteristics consistent with development of electrolyte leakage pathways over time. Additionally, measurements of maximum cathodal potential excursion indicated that only a relatively small fraction of electrodes (10-35% at 1 and 24 wk postimplantation) were capable of delivering relevant currents (20 µA at 4 nC/ph) without exceeding negative or positive electrochemical potential limits. In total, our findings suggest mainly abiotic failure modes, including mechanical wire breakage as well as degradation of conducting and insulating substrates. NEW & NOTEWORTHY Multisite implantable electrode arrays serve as a tool to record cortical network activity and enable electrical stimulation to drive plasticity or provide network feedback. The use of rodent models in these fields is prevalent. We evaluated chronic recording and electrochemical performance of 16-channel Utah electrode arrays in rat motor cortex over a period of 6 mo. We primarily observed abiotic failure modes suggestive of mechanical wire breakage and/or degradation of insulation.

Chronic softening spinal cord stimulation arrays.

OBJECTIVE: We sought to develop a cervical spinal cord stimulator for the rat that is durable, stable, and does not perturb the underlying spinal cord. APPROACH: We created a softening spinal cord stimulation (SCS) array made from shape memory polymer (SMP)-based flexible electronics. We developed a new photolithographic process to pattern high surface area titanium nitride (TiN) electrodes onto gold (Au) interconnects. The thiol-ene acrylate polymers are stiff at room temperature and soften following implantation into the body. Durability was measured by the duration the devices produced effective stimulation and by accelerated aging in vitro. Stability was measured by the threshold to provoke an electromyogram (EMG) muscle response and by measuring impedance using electrochemical impedance spectroscopy (EIS). In addition, spinal cord modulation of motor cortex potentials was measured. The spinal column and implanted arrays were imaged with MRI ex vivo, and histology for astrogliosis and immune reaction was performed. MAIN RESULTS: For durability, the design of the arrays was modified over three generations to create an array that demonstrated activity up to 29 weeks. SCS arrays showed no significant degradation over a simulated 29 week period of accelerated aging. For stability, the threshold for provoking an EMG rose in the first few weeks and then remained stable out to 16 weeks; the impedance showed a similar rise early with stability thereafter. Spinal cord stimulation strongly enhanced motor cortex potentials throughout. Upon explantation, device performance returned to pre-implant levels, indicating that biotic rather than abiotic processes were the cause of changing metrics. MRI and histology showed that softening SCS produced less tissue deformation than Parylene-C arrays. There was no significant astrogliosis or immune reaction to either type of array. SIGNIFICANCE: Softening SCS arrays meet the needs for research-grade devices in rats and could be developed into human devices in the future.

Amorphous silicon carbide ultramicroelectrode arrays for neural stimulation and recording.

OBJECTIVE: Foreign body response to indwelling cortical microelectrodes limits the reliability of neural stimulation and recording, particularly for extended chronic applications in behaving animals. The extent to which this response compromises the chronic stability of neural devices depends on many factors including the materials used in the electrode construction, the size, and geometry of the indwelling structure. Here, we report on the development of microelectrode arrays (MEAs) based on amorphous silicon carbide (a-SiC). APPROACH: This technology utilizes a-SiC for its chronic stability and employs semiconductor manufacturing processes to create MEAs with small shank dimensions. The a-SiC films were deposited by plasma enhanced chemical vapor deposition and patterned by thin-film photolithographic techniques. To improve stimulation and recording capabilities with small contact areas, we investigated low impedance coatings on the electrode sites. The assembled devices were characterized in phosphate buffered saline for their electrochemical properties. MAIN RESULTS: MEAs utilizing a-SiC as both the primary structural element and encapsulation were fabricated successfully. These a-SiC MEAs had 16 penetrating shanks. Each shank has a cross-sectional area less than 60 µm2 and electrode sites with a geometric surface area varying from 20 to 200 µm2. Electrode coatings of TiN and SIROF reduced 1 kHz electrode impedance to less than 100 kΩ from ~2.8 MΩ for 100 µm2 Au electrode sites and increased the charge injection capacities to values greater than 3 mC cm-2. Finally, we demonstrated functionality by recording neural activity from basal ganglia nucleus of Zebra Finches and motor cortex of rat. SIGNIFICANCE: The a-SiC MEAs provide a significant advancement in the development of microelectrodes that over the years has relied on silicon platforms for device manufacture. These flexible a-SiC MEAs have the potential for decreased tissue damage and reduced foreign body response. The technique is promising and has potential for clinical translation and large scale manufacturing.

Metamorphic Superomniphobic Surfaces.

Superomniphobic surfaces are extremely repellent to virtually all liquids. By combining superomniphobicity and shape memory effect, metamorphic superomniphobic (MorphS) surfaces that transform their morphology in response to heat are developed. Utilizing the MorphS surfaces, the distinctly different wetting transitions of liquids with different surface tensions are demonstrated and the underlying physics is elucidated. Both ex situ and in situ wetting transitions on the MorphS surfaces are solely due to transformations in morphology of the surface texture. It is envisioned that the robust MorphS surfaces with reversible wetting transition will have a wide range of applications including rewritable liquid patterns, controlled drug release systems, lab-on-a-chip devices, and biosensors.

Plasmonic amplifiers: engineering giant light enhancements by tuning resonances in multiscale plasmonic nanostructures.

The unique ability of plasmonic nanostructures to guide, enhance, and manipulate subwavelength light offers multiple novel applications in chemical and biological sensing, imaging, and photonic microcircuitry. Here the reproducible, giant light amplification in multiscale plasmonic structures is demonstrated. These structures combine strongly coupled components of different dimensions and topologies that resonate at the same optical frequency. A light amplifier is constructed using a silver mirror carrying light-enhancing surface plasmons, dielectric gratings forming distributed Bragg cavities on top of the mirror, and gold nanoparticle arrays self-assembled into the grating grooves. By tuning the resonances of the individual components to the same frequency, multiple enhancement of the light intensity in the nanometer gaps between the particles is achieved. Using a monolayer of benzenethiol molecules on this structure, an average SERS enhancement factor ∼108 is obtained, and the maximum enhancement in the interparticle hot-spots is ∼3 × 10¹°, in good agreement with FDTD calculations. The high enhancement factor, large density of well-ordered hot-spots, and good fidelity of the SERS signal make this design a promising platform for quantitative SERS sensing, optical detection, efficient solid state lighting, advanced photovoltaics, and other emerging photonic applications.

Self-assembled large Au nanoparticle arrays with regular hot spots for SERS.

The cost-effective self-assembly of 80 nm Au nanoparticles (NPs) into large-domain, hexagonally close-packed arrays for high-sensitivity and high-fidelity surface-enhanced Raman spectroscopy (SERS) is demonstrated. These arrays exhibit specific optical resonances due to strong interparticle coupling, which are well reproduced by finite-difference time-domain (FDTD) simulations. The gaps between NPs form a regular lattice of hot spots that enable a large amplification of both photoluminescence and Raman signals. At smaller wavelengths the hot spots are extended away from the minimum-gap positions, which allows SERS of larger analytes that do not fit into small gaps. Using CdSe quantum dots (QDs) a 3-5 times larger photoluminescence enhancement than previously reported is experimentally demonstrated and an unambiguous estimate of the electromagnetic SERS enhancement factor of ≈10(4) is obtained by direct scanning electron microscopy imaging of QDs responsible for the Raman signal. Much stronger enhancement of ≈10(8) is obtained at larger wavelengths for benzenethiol molecules penetrating the NP gaps.