Electrochemical Roughening of Thin-Film Platinum for Neural Probe Arrays and Biosensing Applications
Abstract
In this work, we report a method for electrochemical roughening of thin-film platinum (Pt) electrodes that increases active surface area, decreases electrode impedance, increases charge injection capacity, increases sensitivity of biosensors and improves adhesion of electrochemically deposited films. First, a well-established technique for electrochemical roughening of thick Pt electrodes (wires and foils) by oxidation-reduction pulses was modified for use on thin-film Pt. Optimal roughening of thin-film Pt electrodes with this established protocol in a sulfuric acid solution was found to occur at about four times lower frequency than that typically used for thick Pt. This modification in established procedure created a 21x surface area increase but showed nanoscale cracks from inter-grain Pt dissolution that compromised film integrity. A crack free surface with Pt nanocrystal re-deposition (20–30 nm in size) and higher enhancement in surface area (44x) was obtained when the electrolyte was switched to a non-adsorbing perchloric acid solution. These electrochemically roughened electrodes have charge injection limits comparable to titanium nitride and just below carbon nanotube-based materials. Roughened microelectrodes showed a 2.8x increase in sensitivity to hydrogen peroxide detection, indicative of improved enzymatic biosensor performance. Platinum iridium and iridium oxide coatings on these roughened surfaces showed an improvement in adhesion.
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1464289
- Alternate Identifier(s):
- OSTI ID: 1467810
- Report Number(s):
- LLNL-JRNL-746398
Journal ID: ISSN 0013-4651; /jes/165/12/G3125.atom
- Grant/Contract Number:
- AC52-07NA27344; 16-ERD-035
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 12; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 42 ENGINEERING; 77 NANOSCIENCE AND NANOTECHNOLOGY; 59 BASIC BIOLOGICAL SCIENCES; Electrochemical roughening; microelectrode; neuromodulation
Citation Formats
Ivanovskaya, Anna N., Belle, Anna M., Yorita, Allison M., Qian, Fang, Chen, Supin, Tooker, Angela, Lozada, Rose García, Dahlquist, Dylan, and Tolosa, Vanessa. Electrochemical Roughening of Thin-Film Platinum for Neural Probe Arrays and Biosensing Applications. United States: N. p., 2018.
Web. doi:10.1149/2.0171812jes.
Ivanovskaya, Anna N., Belle, Anna M., Yorita, Allison M., Qian, Fang, Chen, Supin, Tooker, Angela, Lozada, Rose García, Dahlquist, Dylan, & Tolosa, Vanessa. Electrochemical Roughening of Thin-Film Platinum for Neural Probe Arrays and Biosensing Applications. United States. https://doi.org/10.1149/2.0171812jes
Ivanovskaya, Anna N., Belle, Anna M., Yorita, Allison M., Qian, Fang, Chen, Supin, Tooker, Angela, Lozada, Rose García, Dahlquist, Dylan, and Tolosa, Vanessa. Fri .
"Electrochemical Roughening of Thin-Film Platinum for Neural Probe Arrays and Biosensing Applications". United States. https://doi.org/10.1149/2.0171812jes.
@article{osti_1464289,
title = {Electrochemical Roughening of Thin-Film Platinum for Neural Probe Arrays and Biosensing Applications},
author = {Ivanovskaya, Anna N. and Belle, Anna M. and Yorita, Allison M. and Qian, Fang and Chen, Supin and Tooker, Angela and Lozada, Rose García and Dahlquist, Dylan and Tolosa, Vanessa},
abstractNote = {In this work, we report a method for electrochemical roughening of thin-film platinum (Pt) electrodes that increases active surface area, decreases electrode impedance, increases charge injection capacity, increases sensitivity of biosensors and improves adhesion of electrochemically deposited films. First, a well-established technique for electrochemical roughening of thick Pt electrodes (wires and foils) by oxidation-reduction pulses was modified for use on thin-film Pt. Optimal roughening of thin-film Pt electrodes with this established protocol in a sulfuric acid solution was found to occur at about four times lower frequency than that typically used for thick Pt. This modification in established procedure created a 21x surface area increase but showed nanoscale cracks from inter-grain Pt dissolution that compromised film integrity. A crack free surface with Pt nanocrystal re-deposition (20–30 nm in size) and higher enhancement in surface area (44x) was obtained when the electrolyte was switched to a non-adsorbing perchloric acid solution. These electrochemically roughened electrodes have charge injection limits comparable to titanium nitride and just below carbon nanotube-based materials. Roughened microelectrodes showed a 2.8x increase in sensitivity to hydrogen peroxide detection, indicative of improved enzymatic biosensor performance. Platinum iridium and iridium oxide coatings on these roughened surfaces showed an improvement in adhesion.},
doi = {10.1149/2.0171812jes},
journal = {Journal of the Electrochemical Society},
number = 12,
volume = 165,
place = {United States},
year = {Fri Aug 10 00:00:00 EDT 2018},
month = {Fri Aug 10 00:00:00 EDT 2018}
}
https://doi.org/10.1149/2.0171812jes
Web of Science
Works referenced in this record:
Neural Stimulation with a Carbon Nanotube Microelectrode Array
journal, September 2006
- Wang, Ke; Fishman, Harvey A.; Dai, Hongjie
- Nano Letters, Vol. 6, Issue 9
Pseudo-Single-Crystal Electrochemistry on Polycrystalline Electrodes: Visualizing Activity at Grains and Grain Boundaries on Platinum for the Fe 2+ /Fe 3+ Redox Reaction
journal, February 2013
- Aaronson, Barak D. B.; Chen, Chang-Hui; Li, Hongjiao
- Journal of the American Chemical Society, Vol. 135, Issue 10
Silicon Wafer-Based Platinum Microelectrode Array Biosensor for Near Real-Time Measurement of Glutamate in Vivo
journal, August 2008
- Wassum, Kate; Tolosa, Vanessa; Wang, Jianjun
- Sensors, Vol. 8, Issue 8
Long-Term Stable Adhesion for Conducting Polymers in Biomedical Applications: IrOx and Nanostructured Platinum Solve the Chronic Challenge
journal, December 2016
- Boehler, Christian; Oberueber, Felix; Schlabach, Sabine
- ACS Applied Materials & Interfaces, Vol. 9, Issue 1
Investigation of surface-enhanced Raman scattering from platinum electrodes using a confocal Raman microscope: dependence of surface roughening pretreatment
journal, May 1998
- Cai, W. B.; Ren, B.; Li, X. Q.
- Surface Science, Vol. 406, Issue 1-3
Electrochemically Roughened Palladium Electrodes for Surface-Enhanced Raman Spectroscopy: Methodology, Mechanism, and Application
journal, February 2007
- Liu, Zheng; Yang, Zhi-Lin; Cui, Li
- The Journal of Physical Chemistry C, Vol. 111, Issue 4
Neural recording and modulation technologies
journal, January 2017
- Chen, Ritchie; Canales, Andres; Anikeeva, Polina
- Nature Reviews Materials, Vol. 2, Issue 2
Advanced Neurotechnologies for Chronic Neural Interfaces: New Horizons and Clinical Opportunities
journal, November 2008
- Kipke, D. R.; Shain, W.; Buzsaki, G.
- Journal of Neuroscience, Vol. 28, Issue 46
Neural Stimulation and Recording Electrodes
journal, August 2008
- Cogan, Stuart F.
- Annual Review of Biomedical Engineering, Vol. 10, Issue 1, p. 275-309
Raman spectra of pyridine adsorbed at a silver electrode
journal, May 1974
- Fleischmann, M.; Hendra, P. J.; McQuillan, A. J.
- Chemical Physics Letters, Vol. 26, Issue 2, p. 163-166
Ferrocene-mediated enzyme electrode for amperometric determination of glucose
journal, April 1984
- Cass, Anthony E. G.; Davis, Graham.; Francis, Graeme D.
- Analytical Chemistry, Vol. 56, Issue 4
Determination of the Real Surface Area of Pt Electrodes by Hydrogen Adsorption Using Cyclic Voltammetry
journal, September 2000
- Doña Rodríguez, José M.; Herrera Melián, José Alberto; Pérez Peña, Jesús
- Journal of Chemical Education, Vol. 77, Issue 9
Substrate dependent stability of conducting polymer coatings on medical electrodes
journal, September 2012
- Green, Rylie A.; Hassarati, Rachelle T.; Bouchinet, Lucie
- Biomaterials, Vol. 33, Issue 25
Electrical Stimulation with Pt Electrodes: II-Estimation of Maximum Surface Redox (Theoretical Non-Gassing) Limits
journal, September 1977
- Brummer, S. B.; Turner, M. J.
- IEEE Transactions on Biomedical Engineering, Vol. BME-24, Issue 5
Chronic electrical stimulation of the auditory nerve using high surface area (HiQ) platinum electrodes
journal, September 2001
- Tykocinski, Michael; Duan, Yvonne; Tabor, Bruce
- Hearing Research, Vol. 159, Issue 1-2
A Review of Organic and Inorganic Biomaterials for Neural Interfaces
journal, February 2014
- Fattahi, Pouria; Yang, Guang; Kim, Gloria
- Advanced Materials, Vol. 26, Issue 12
Polymers for neural implants
journal, November 2010
- Hassler, Christina; Boretius, Tim; Stieglitz, Thomas
- Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 1, p. 18-33
Fuzzy gold electrodes for lowering impedance and improving adhesion with electrodeposited conducting polymer films
journal, February 2003
- Cui, Xinyan; Martin, David C.
- Sensors and Actuators A: Physical, Vol. 103, Issue 3
The real condition of oxidized pt electrodes
journal, November 1973
- Tilak, B. V.; Conway, B. E.; Angerstein-Kozlowska, H.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 48, Issue 1
Chronic neural recordings using silicon microelectrode arrays electrochemically deposited with a poly(3,4-ethylenedioxythiophene) (PEDOT) film
journal, March 2006
- Ludwig, Kip A.; Uram, Jeffrey D.; Yang, Junyan
- Journal of Neural Engineering, Vol. 3, Issue 1
Anodically Electrodeposited Iridium Oxide Films (AEIROF) from Alkaline Solutions for Electrochromic Display Devices
journal, April 1989
- Yamanaka, Kazusuke
- Japanese Journal of Applied Physics, Vol. 28, Issue Part 1, No. 4
Electrodeposited iridium oxide for neural stimulation and recording electrodes
journal, March 2001
- Meyer, R. D.; Cogan, S. F.; Nguyen, T. H.
- IEEE Transactions on Neural Systems and Rehabilitation Engineering, Vol. 9, Issue 1
Electrical stimulation with Pt electrodes. VIII. Electrochemically safe charge injection limits with 0.2 ms pulses (neuronal application)
journal, January 1990
- Rose, T. L.; Robblee, L. S.
- IEEE Transactions on Biomedical Engineering, Vol. 37, Issue 11
In vitro electrical properties for iridium oxide versus titanium nitride stimulating electrodes
journal, December 2002
- Weiland, J. D.; Anderson, D. J.; Humayun, M. S.
- IEEE Transactions on Biomedical Engineering, Vol. 49, Issue 12
Laser patterning of platinum electrodes for safe neurostimulation
journal, September 2014
- Green, R. A.; Matteucci, P. B.; Dodds, C. W. D.
- Journal of Neural Engineering, Vol. 11, Issue 5
Effects of electrolytes used in roughening gold substrates by oxidation–reduction cycles on surface-enhanced Raman scattering
journal, December 2005
- Liu, Yu-Chuan; Wang, Chee-Chan; Tsai, Chun-En
- Electrochemistry Communications, Vol. 7, Issue 12
Thin film platinum cuff electrodes for neurostimulation: in vitro approach of safe neurostimulation parameters
journal, June 2004
- Mailley, Sophie; Hyland, Marc; Mailley, Pascal
- Bioelectrochemistry, Vol. 63, Issue 1-2
Investigating the Interfacial Properties of Electrochemically Roughened Platinum Electrodes for Neural Stimulation
journal, February 2015
- Weremfo, Alexander; Carter, Paul; Hibbert, D. Brynn
- Langmuir, Vol. 31, Issue 8
Electrode modifications to lower electrode impedance and improve neural signal recording sensitivity
journal, September 2015
- Chung, T.; Wang, J. Q.; Wang, J.
- Journal of Neural Engineering, Vol. 12, Issue 5
Electrodeposition and Characterization of Thin-Film Platinum-Iridium Alloys for Biological Interfaces
journal, January 2011
- Petrossians, Artin; Whalen III, John J.; Weiland, James D.
- Journal of The Electrochemical Society, Vol. 158, Issue 5
Microfabricated, amperometric, enzyme-based biosensors for in vivo applications
journal, March 2016
- Weltin, Andreas; Kieninger, Jochen; Urban, Gerald A.
- Analytical and Bioanalytical Chemistry, Vol. 408, Issue 17
Electron transfer processes occurring on platinum neural stimulating electrodes: a tutorial on the i ( V e ) profile
journal, August 2016
- Kumsa, Doe W.; Bhadra, Narendra; Hudak, Eric M.
- Journal of Neural Engineering, Vol. 13, Issue 5
Flexible and stretchable micro-electrodes for in vitro and in vivo neural interfaces
journal, June 2010
- Lacour, Stéphanie P.; Benmerah, Samia; Tarte, Edward
- Medical & Biological Engineering & Computing, Vol. 48, Issue 10, p. 945-954