FemtoAmpere Integrated Current Preamplifier for Low Noise and Wide Bandwidth Electrochemistry with Nanoelectrodes

Abstract The direct tracking of the potential-induced modulation of the double layer capacitance (100 mV bias steps resulting in 1.2 fF variations) of Pt nanoelectrodes (100 nm diameter) in physiological solution with sub-fF resolution and 10 ms response time is reported. This result is an example of the enhanced performance achieved thanks to an integrated CMOS current preamplifier used as an add-on for standard bench-top electrochemical instrumentation. The chip provides a current amplification of 103 over the wide frequency range DC-2 MHz and can be placed at the input of a current-to-voltage converter to reach higher gains. Thanks to its millimetric size it drastically reduces the input stray capacitance of the connection cables to the electrode, offering superior noise performance such as 0.55 fA (rms) current resolution with 1 Hz bandwidth demonstrated in the detection of 1.5 fA current steps. The improvement in performance of state-of-art commercial potentiostats is also reported: the largest measurable impedance is increased by two orders of magnitude (up to 100 GΩ with only 10 mV applied and 0.125 s averaging time) and the impedance noise in time tracking is reduced 35 times. This module has been developed for nano-electrochemical and bio-sensing applications but can be profitably used in all the situations in which few electrons are exchanged at the interface, either since the electrode area is nanometric or since the concentration of the redox species is extremely low.

[1]  Vincent Vivier,et al.  Determination of effective capacitance and film thickness from constant-phase-element parameters , 2010 .

[2]  Marco Carminati,et al.  Accuracy and resolution limits in quartz and silicon substrates with microelectrodes for electrochemical biosensors , 2012 .

[3]  Marco Carminati,et al.  Ultra-low-noise CMOS current preamplifier from DC to 1 MHz , 2009 .

[4]  Christian Amatore,et al.  Zeptomole voltammetric detection and electron-transfer rate measurements using platinum electrodes of nanometer dimensions. , 2003, Analytical chemistry.

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

[6]  Marco Carminati,et al.  Attofarad resolution potentiostat for electrochemical measurements on nanoscale biomolecular interfacial systems. , 2009, The Review of scientific instruments.

[7]  Jean-Marc Noël,et al.  Nanoelectrodes for determination of reactive oxygen and nitrogen species inside murine macrophages , 2012, Proceedings of the National Academy of Sciences.

[8]  K. Shepard,et al.  Integrated nanopore sensing platform with sub-microsecond temporal resolution , 2012, Nature Methods.

[9]  Christian Amatore,et al.  When voltammetry reaches nanoseconds. , 2005, Analytical Chemistry.

[10]  R. Bashir,et al.  Nanopore sensors for nucleic acid analysis. , 2011, Nature nanotechnology.

[11]  Arto Heiskanen,et al.  Fully automated microchip system for the detection of quantal exocytosis from single and small ensembles of cells. , 2008, Lab on a chip.

[12]  Marco Carminati,et al.  ZeptoFarad capacitance detection with a miniaturized CMOS current front-end for nanoscale sensors , 2011 .

[13]  T. Albrecht Electrochemical tunnelling sensors and their potential applications , 2012, Nature Communications.

[14]  F. Sigworth,et al.  Microchip technology in ion-channel research , 2005, IEEE Transactions on NanoBioscience.

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

[16]  C. Leygraf,et al.  Investigation of interfacial capacitance of Pt, Ti and TiN coated electrodes by electrochemical impedance spectroscopy. , 2002, Biomolecular engineering.

[17]  S Mohammadi,et al.  A nanofluidic channel with embedded transverse nanoelectrodes , 2009, Nanotechnology.

[18]  N. Raouafi,et al.  Do molecular conductances correlate with electrochemical rate constants? Experimental insights. , 2011, Journal of the American Chemical Society.

[19]  M. W. Breiter,et al.  Measurements of large impedances in a wide temperature and frequency range , 1996 .

[20]  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.