Bottom-up SiO2 embedded carbon nanotube electrodes with superior performance for integration in implantable neural microsystems.

The reliable integration of carbon nanotube (CNT) electrodes in future neural probes requires a proper embedding of the CNTs to prevent damage and toxic contamination during fabrication and also to preserve their mechanical integrity during implantation. Here we describe a novel bottom-up embedding approach where the CNT microelectrodes are encased in SiO(2) and Parylene C with lithographically defined electrode openings. Vertically aligned CNTs are grown on microelectrode arrays using low-temperature plasma-enhanced chemical vapor deposition compatible with wafer-scale CMOS processing. Electrodes with 5, 10, and 25 μm diameter are realized. The CNT electrodes are characterized by electrochemical impedance spectroscopy and cyclic voltammetry and compared against cofabricated Pt and TiN electrodes. The superior performance of the CNTs in terms of impedance (≤4.8 ± 0.3 kΩ at 1 kHz) and charge-storage capacity (≥513.9 ± 61.6 mC/cm(2)) is attributed to an increased wettability caused by the removal of the SiO(2) embedding in buffered hydrofluoric acid. Infrared spectroscopy reveals an unaltered chemical fingerprint of the CNTs after fabrication. Impedance monitoring during biphasic current pulsing with increasing amplitudes provides clear evidence of the onset of gas evolution at CNT electrodes. Stimulation is accordingly considered safe for charge densities ≤40.7 mC/cm(2). In addition, prolonged stimulation with 5000 biphasic current pulses at 8.1, 40.7, and 81.5 mC/cm(2) increases the CNT electrode impedance at 1 kHz only by 5.5, 1.2, and 12.1%, respectively. Finally, insertion of CNT electrodes with and without embedding into rat brains demonstrates that embedded CNTs are mechanically more stable than non-embedded CNTs.

[1]  Luciano Fadiga,et al.  Superior electrochemical performance of carbon nanotubes directly grown on sharp microelectrodes. , 2011, ACS nano.

[2]  J. W. Schultze,et al.  Passivation and corrosion of microelectrode arrays , 1999 .

[3]  R Saito,et al.  Infrared-active vibrational modes of single-walled carbon nanotubes. , 2005, Physical review letters.

[4]  Luciano Fadiga,et al.  Carbon nanotube composite coating of neural microelectrodes preferentially improves the multiunit signal-to-noise ratio , 2011, Journal of neural engineering.

[5]  Daryl R Kipke,et al.  Theoretical analysis of intracortical microelectrode recordings , 2011, Journal of neural engineering.

[6]  A CMOS Compatible Carbon Nanotube Growth Approach , 2010 .

[7]  Darren J. Martin,et al.  THE BIOCOMPATIBILITY OF CARBON NANOTUBES , 2006 .

[8]  Li Han Chen,et al.  Electrochemical properties and myocyte interaction of carbon nanotube microelectrodes. , 2010, Nano letters.

[9]  B. Conway Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications , 1999 .

[10]  F. Toma,et al.  Multiwalled carbon-nanotube-functionalized microelectrode arrays fabricated by microcontact printing: platform for studying chemical and electrical neuronal signaling. , 2011, Small.

[11]  Eshel Ben-Jacob,et al.  Electro-chemical and biological properties of carbon nanotube based multi-electrode arrays , 2007, Nanotechnology.

[12]  M. Meyyappan,et al.  Carbon Nanotube Nanoelectrode Array for Ultrasensitive DNA Detection , 2003 .

[13]  Charles M. Lieber,et al.  Nanomaterials for Neural Interfaces , 2009 .

[14]  Un Jeong Kim,et al.  Raman and IR spectroscopy of chemically processed single-walled carbon nanotubes. , 2005, Journal of the American Chemical Society.

[15]  B. Botterman,et al.  Carbon nanotube coating improves neuronal recordings. , 2008, Nature nanotechnology.

[16]  Shuo Chen,et al.  High-power lithium batteries from functionalized carbon-nanotube electrodes. , 2010, Nature nanotechnology.

[17]  Weileun Fang,et al.  Flexible carbon nanotubes electrode for neural recording. , 2009, Biosensors & bioelectronics.

[18]  Henry Markram,et al.  Substrate Arrays of Iridium Oxide Microelectrodes for in Vitro Neuronal Interfacing , 2008, Front. Neuroeng..

[19]  M. Heyns,et al.  Integration and electrical characterization of carbon nanotube via interconnects , 2011 .

[20]  L. Forró,et al.  Cellular toxicity of carbon-based nanomaterials. , 2006, Nano letters.

[21]  J. Thomas Mortimer,et al.  The Role of Oxygen Reduction in Electrical Stimulation of Neural Tissue , 1994 .

[22]  Hongjie Dai,et al.  Neural stimulation with a carbon nanotube microelectrode array. , 2006, Nano letters.

[23]  J. Csicsvari,et al.  Massively parallel recording of unit and local field potentials with silicon-based electrodes. , 2003, Journal of neurophysiology.

[24]  N. H. Lovell,et al.  Novel neural interface for implant electrodes: improving electroactivity of polypyrrole through MWNT incorporation , 2008, Journal of materials science. Materials in medicine.

[25]  Hsin Chen,et al.  An active, flexible carbon nanotube microelectrode array for recording electrocorticograms , 2011, Journal of neural engineering.

[26]  W. Smyrl,et al.  Characterization of anodic oxide film formed on tin coating in neutral borate buffer solution , 1998 .

[27]  M. Moffitt,et al.  Model-based analysis of cortical recording with silicon microelectrodes , 2005, Clinical Neurophysiology.

[28]  Robert C. Haddon,et al.  Molecular functionalization of carbon nanotubes and use as substrates for neuronal growth , 2000, Journal of Molecular Neuroscience.

[29]  S. Musa,et al.  Coulometric detection of irreversible electrochemical reactions occurring at Pt microelectrodes used for neural stimulation. , 2011, Analytical chemistry.

[30]  Evelyne Sernagor,et al.  Carbon Nanotube Electrodes for Effective Interfacing with Retinal Tissue , 2009, Front. Neuroeng..

[31]  Stuart F Cogan,et al.  Over-pulsing degrades activated iridium oxide films used for intracortical neural stimulation , 2004, Journal of Neuroscience Methods.

[32]  Manhong Liu,et al.  Chemical modification of single-walled carbon nanotubes with peroxytrifluoroacetic acid , 2005 .

[33]  Rajmohan Bhandari,et al.  Neural electrode degradation from continuous electrical stimulation: Comparison of sputtered and activated iridium oxide , 2010, Journal of Neuroscience Methods.

[34]  P. Haldar,et al.  Electrochemical oxidation behavior of titanium nitride based electrocatalysts under PEM fuel cell conditions , 2010 .

[35]  P. Gubellini,et al.  Deep brain stimulation in neurological diseases and experimental models: From molecule to complex behavior , 2009, Progress in Neurobiology.

[36]  Wendy G. Pell,et al.  Power limitations of supercapacitor operation associated with resistance and capacitance distribution in porous electrode devices , 2002 .

[37]  B. Xing,et al.  Adsorption mechanisms of organic chemicals on carbon nanotubes. , 2008, Environmental science & technology.

[38]  G. Socrates,et al.  Infrared and Raman characteristic group frequencies : tables and charts , 2001 .

[39]  Douglas B. Shire,et al.  Contribution of Oxygen Reduction to Charge Injection on Platinum and Sputtered Iridium Oxide Neural Stimulation Electrodes , 2010, IEEE Transactions on Biomedical Engineering.

[40]  Kevin J. Otto,et al.  Poly(3,4-ethylenedioxythiophene) as a Micro-Neural Interface Material for Electrostimulation , 2009, Front. Neuroeng..

[41]  James D. Weiland,et al.  Electrochemical Characterization of Charge Injection at Electrodeposited Platinum Electrodes in Phosphate Buffered Saline , 2006 .

[42]  Yung-Chan Chen,et al.  Hydrophilic modification of neural microelectrode arrays based on multi-walled carbon nanotubes , 2010, Nanotechnology.

[43]  Ray H. Baughman,et al.  Electrochemical Characterization of Single‐Walled Carbon Nanotube Electrodes , 2000 .

[44]  R A Normann,et al.  Chronic intracortical microstimulation (ICMS) of cat sensory cortex using the Utah Intracortical Electrode Array. , 1999, IEEE transactions on rehabilitation engineering : a publication of the IEEE Engineering in Medicine and Biology Society.

[45]  James M Tour,et al.  Biocompatibility of native and functionalized single-walled carbon nanotubes for neuronal interface. , 2006, Journal of nanoscience and nanotechnology.

[46]  Jin Zhai,et al.  Self-assembly of large-scale micropatterns on aligned carbon nanotube films. , 2004, Angewandte Chemie.

[47]  Y. Tai,et al.  Wafer-Level Parylene Packaging With Integrated RF Electronics for Wireless Retinal Prostheses , 2010, Journal of Microelectromechanical Systems.

[48]  E. Ben-Jacob,et al.  Engineered neuronal circuits shaped and interfaced with carbon nanotube microelectrode arrays , 2009, Biomedical microdevices.

[49]  John Newman,et al.  Current Distributions on Recessed Electrodes , 1991 .

[50]  J. Mink,et al.  Deep brain stimulation. , 2006, Annual review of neuroscience.

[51]  M. D. Rooij,et al.  Electrochemical Methods: Fundamentals and Applications , 2003 .

[52]  Jon A. Mukand,et al.  Neuronal ensemble control of prosthetic devices by a human with tetraplegia , 2006, Nature.

[53]  K. Watson,et al.  Rapid, solventless, bulk preparation of metal nanoparticle-decorated carbon nanotubes. , 2009, ACS nano.

[54]  Alberto Paleari,et al.  Glycine-Spacers Influence Functional Motifs Exposure and Self-Assembling Propensity of Functionalized Substrates Tailored for Neural Stem Cell Cultures , 2009, Front. Neuroeng..

[55]  M. Prato,et al.  Carbon nanotube substrates boost neuronal electrical signaling. , 2005, Nano letters.

[56]  Yung-Chan Chen,et al.  Flexible UV‐Ozone‐Modified Carbon Nanotube Electrodes for Neuronal Recording , 2010, Advanced materials.

[57]  H. Markram,et al.  Interfacing Neurons with Carbon Nanotubes: Electrical Signal Transfer and Synaptic Stimulation in Cultured Brain Circuits , 2007, The Journal of Neuroscience.

[58]  R C Black,et al.  Dissolution of smooth platinum electrodes in biological fluids. , 1980, Applied neurophysiology.

[59]  M. Metikoš-huković,et al.  Electrochemical and thermal oxidation of TiN coatings studied by XPS , 1995 .

[60]  G. Gabriel,et al.  Easily made single-walled carbon nanotube surface microelectrodes for neuronal applications. , 2009, Biosensors & bioelectronics.

[61]  Robert K. Shepherd,et al.  Stimulus Induced pH Changes in Cochlear Implants: An In Vitro and In Vivo Study , 2001, Annals of Biomedical Engineering.

[62]  C. Sow,et al.  Tailoring wettability change on aligned and patterned carbon nanotube films for selective assembly. , 2007, Journal of Physical Chemistry B.

[63]  A. Downard,et al.  Patterned arrays of vertically aligned carbon nanotube microelectrodes on carbon films prepared by thermal chemical vapor deposition. , 2008, Analytical chemistry.

[64]  David C. Martin,et al.  Layered carbon nanotube-polyelectrolyte electrodes outperform traditional neural interface materials. , 2009, Nano letters.

[65]  J. McHardy,et al.  Electrical stimulation with Pt electrodes. VII. Dissolution of Pt electrodes during electrical stimulation of the cat cerebral cortex , 1983, Journal of Neuroscience Methods.

[66]  Chris Boldt,et al.  Creating low-impedance tetrodes by electroplating with additives. , 2009, Sensors and actuators. A, Physical.

[67]  S. Cogan Neural stimulation and recording electrodes. , 2008, Annual review of biomedical engineering.

[68]  Jae-Hee Han,et al.  Enhanced field emission properties of thin-multiwalled carbon nanotubes: Role of SiOx coating , 2006 .