Nanocavity crossbar arrays for parallel electrochemical sensing on a chip

Summary We introduce a novel device for the mapping of redox-active compounds at high spatial resolution based on a crossbar electrode architecture. The sensor array is formed by two sets of 16 parallel band electrodes that are arranged perpendicular to each other on the wafer surface. At each intersection, the crossing bars are separated by a ca. 65 nm high nanocavity, which is stabilized by the surrounding passivation layer. During operation, perpendicular bar electrodes are biased to potentials above and below the redox potential of species under investigation, thus, enabling repeated subsequent reactions at the two electrodes. By this means, a redox cycling current is formed across the gap that can be measured externally. As the nanocavity devices feature a very high current amplification in redox cycling mode, individual sensing spots can be addressed in parallel, enabling high-throughput electrochemical imaging. This paper introduces the design of the device, discusses the fabrication process and demonstrates its capabilities in sequential and parallel data acquisition mode by using a hexacyanoferrate probe.

[1]  R. Wightman Probing Cellular Chemistry in Biological Systems with Microelectrodes , 2006, Science.

[2]  K. Ino,et al.  Addressable electrochemiluminescence detection system based on redox-cycling of Ru(bpy)(3)(2+). , 2010, Chemical communications.

[3]  Pradyumna S. Singh,et al.  Stochasticity in single-molecule nanoelectrochemistry: origins, consequences, and solutions. , 2012, ACS nano.

[4]  Hitoshi Shiku,et al.  Addressable electrode array device with IDA electrodes for high-throughput detection. , 2011, Lab on a chip.

[5]  Amperometric detection of DNA hybridization using a multi-point, addressable electrochemical device , 2011 .

[6]  Osamu Niwa,et al.  Electroanalysis with interdigitated array microelectrodes , 1995 .

[7]  I. Fritsch,et al.  Signal amplification in a microchannel from redox cycling with varied electroactive configurations of an individually addressable microband electrode array. , 2010, Analytical chemistry.

[8]  I. Fritsch,et al.  Detection of dopamine in the presence of excess ascorbic acid at physiological concentrations through redox cycling at an unmodified microelectrode array , 2013, Analytical and Bioanalytical Chemistry.

[9]  Rafael Yuste,et al.  Nanotools for neuroscience and brain activity mapping. , 2013, ACS nano.

[10]  Bernhard Wolfrum,et al.  Redox cycling in nanofluidic channels using interdigitated electrodes , 2009, Analytical and bioanalytical chemistry.

[11]  Droplet array on local redox cycling-based electrochemical (LRC-EC) chip device. , 2014, Lab on a chip.

[12]  K. Ino,et al.  Electrochemical topography of a cell monolayer with an addressable microelectrode array. , 2010, Chemical communications.

[13]  B. Wolfrum,et al.  On-chip redox cycling techniques for electrochemical detection , 2012 .

[14]  Pradyumna S. Singh,et al.  Single-molecule electrochemistry: present status and outlook. , 2013, Accounts of chemical research.

[15]  Manfred Lindau,et al.  Parallel recording of neurotransmitters release from chromaffin cells using a 10×10 CMOS IC potentiostat array with on-chip working electrodes. , 2013, Biosensors & bioelectronics.

[16]  Jun Wang,et al.  Individually addressable thin-film ultramicroelectrode array for spatial measurements of single vesicle release. , 2013, Analytical chemistry.

[17]  Bernhard Wolfrum,et al.  Nanofluidic redox cycling amplification for the selective detection of catechol. , 2008, Analytical chemistry.

[18]  L. Anderson,et al.  Filar electrodes: steady-state currents and spectroelectrochemistry at twin interdigitated electrodes , 1985 .

[19]  M. Stelzle,et al.  Characterization of Nanopore Electrode Structures as Basis for Amplified Electrochemical Assays , 2006 .

[20]  P. Unwin,et al.  SCANNING ELECTROCHEMICAL MICROSCOPE INDUCED DISSOLUTION : RATE LAW AND REACTION RATE IMAGING FOR DISSOLUTION OF THE (010) FACE OF POTASSIUM FERROCYANI DE TRIHYDRATE IN NONSTOICHIOMETRIC AQUEOUS SOLUTIONS OF THE LATTICE IONS , 1995 .

[21]  Hitoshi Shiku,et al.  An addressable microelectrode array for electrochemical detection. , 2008, Analytical chemistry.

[22]  Boris Hofmann,et al.  Nanocavity redox cycling sensors for the detection of dopamine fluctuations in microfluidic gradients. , 2010, Analytical chemistry.

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

[24]  M. Lindau,et al.  Improved surface-patterned platinum microelectrodes for the study of exocytotic events. , 2009, Analytical chemistry.

[25]  Kevin D. Gillis,et al.  Microwell device for targeting single cells to electrochemical microelectrodes for high-throughput amperometric detection of quantal exocytosis. , 2011, Analytical chemistry.

[26]  H. Shiku,et al.  Topographical and electrochemical nanoscale imaging of living cells using voltage-switching mode scanning electrochemical microscopy , 2012, Proceedings of the National Academy of Sciences.

[27]  Pradyumna S. Singh,et al.  Lithography-based nanoelectrochemistry. , 2011, Analytical chemistry.

[28]  R. Wightman,et al.  Simultaneous monitoring of dopamine concentration at spatially different brain locations in vivo. , 2010, Biosensors & bioelectronics.

[29]  W. Schuhmann,et al.  Single live cell topography and activity imaging with the shear-force-based constant-distance scanning electrochemical microscope. , 2012, Methods in enzymology.

[30]  A. Bard,et al.  Electrochemical Detection of Single Molecules , 1995, Science.

[31]  K. Ino,et al.  Electrochemical gene-function analysis for single cells with addressable microelectrode/microwell arrays. , 2009, Angewandte Chemie.

[32]  Alexey Yakushenko,et al.  Parallel on-chip analysis of single vesicle neurotransmitter release. , 2013, Analytical chemistry.

[33]  Edgar D Goluch,et al.  Stochastic sensing of single molecules in a nanofluidic electrochemical device. , 2011, Nano letters.

[34]  A. Ewing,et al.  Carbon-ring microelectrode arrays for electrochemical imaging of single cell exocytosis: fabrication and characterization. , 2012, Analytical chemistry.

[35]  Dileep Mampallil,et al.  Electrochemical single-molecule detection in aqueous solution using self-aligned nanogap transducers. , 2013, ACS nano.

[36]  Hitoshi Shiku,et al.  Local redox-cycling-based electrochemical chip device with deep microwells for evaluation of embryoid bodies. , 2012, Angewandte Chemie.

[37]  Koichi Aoki,et al.  Quantitative analysis of reversible diffusion-controlled currents of redox soluble species at interdigitated array electrodes under steady-state conditions , 1988 .

[38]  Hitoshi Shiku,et al.  Electrochemical chip integrating scalable ring-ring electrode array to detect secreted alkaline phosphatase. , 2011, The Analyst.