ToF-secondary ion mass-spectrometric study of copper deposition and stripping on directly heated screen-printed gold electrodes

Abstract

We report about a new kind of directly heated gold electrode. All electrodes including a directly heated gold loop electrode, a Ag pseudo reference, and a carbon counter electrode have been screen-printed on a ceramic alumina substrate. Thermal behaviour was studied by potentiometry using either an external or the integrated reference electrode. Stripping voltammetric copper signals were greatly improved at elevated deposition temperature. Secondary ion mass spectrometric studies (ToF-SIMS) revealed that different negative ionic species of copper complexes can be found on the gold electrode surface as a result of ion bombardment during SIMS analysis like Cu, CuCl and CuCl2 . SIMS surface imaging using a fine focussed ion beam over the surface allowed us to obtain ion images (chemical maps) of the analyzed sample. SIMS depth profile analysis of the gold loop electrode was performed after copper deposition at room temperature (23 °C) and at 60 °C. CuCl2 ion was used for the depth profile studies as it has shown the highest intensity among other observed species. Surface spectroscopic analysis, surface imaging and depth profile analysis have shown that the amount of deposited copper species on the gold loop electrode was increased upon increasing electrode temperature during the deposition step. Therefore, the presence of chloride in the solution will hinder underpotential deposition of Cu(0) and lead to badly defined and resolved stripping peaks.

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References

  1. 1.

    Gründler P, Flechsig GU (1998) Deposition and stripping at heated microelectrodes. Arsenic(V) at gold electrode. Electrochim Acta 23:3451–3458

    Google Scholar 

  2. 2.

    Tadesse Zerihun, Gründler P (1996) Electrically heated cylindrical microelectrodes. Determination of lead on Pt by cyclic voltammetry and cathodic stripping analysis. J Electroanal Chem 415:85–88

  3. 3.

    Wang J, Gründler P, Flechsig GU, Jasinski M, Lu J, Wang J, Zhao Z, Tian B (1999) Hot-wire Stripping Potentiometric Measurements of Trace Mercury. Anal Chim Acta 396:33–36

    Google Scholar 

  4. 4.

    Flechsig GU, Korbut O, Gründler P (2001) Investigation of deposition and stripping phenomena at the heated gold wire electrode in comparison to the rotating disk electrode: Copper(II), mercury(II), and arsenic(III). Electroanalysis 13:786–788

    Google Scholar 

  5. 5.

    Jasinski M, Kirbs A, Schmehl M, Gründler P (1999) Heated mercury film electrode for anodic stripping voltammetry. Electrochem Commun 1:26–28

    Google Scholar 

  6. 6.

    Jasinski M, Gründler P, Flechsig GU, Wang J (2001) Anodic stripping voltammetry with a heated mercury film on a screen-printed carbon electrode. Electroanalysis 13:34–36

    Google Scholar 

  7. 7.

    Wang J, Gründler P, Flechsig GU, Jasinski M, Rivas G, Sahlin E, Paz JLL (2000) Stripping analysis of nucleic acids at a heated carbon paste electrode. Anal Chem 72:3752–3756

    Google Scholar 

  8. 8.

    Herzog G, Arrigan DWM (2003) Application of disorganized monolayer films on gold electrodes to the prevention of surfactant inhibition of the voltammetric detection of trace metals via anodic stripping of underpotential deposits: Detection of copper. Anal Chem 75:319–323

    Google Scholar 

  9. 9.

    Herzog G, Arrigan DWM (2003) Comparison of 2-mercaptoethane sulfonate and mercaptoacetic acid disorganized monolayer-coated electrodes for the detection of copper via underpotential deposition-stripping voltammetry. Electroanalysis 15:1302–1306

    Google Scholar 

  10. 10.

    Herzog G, Arrigan DWM (2005) Determination of trace metals by underpotential deposition-stripping voltammetry at solid electrodes. Trends Anal Chem 24:208–217

    Google Scholar 

  11. 11.

    Schröder M, Sohn S, Arlinghaus HF (2004) Investigation of secondary cluster ion emission from self-assembled monolayers of alkanethiols on gold with ToF-SIMS. Appl Surf Sci 231–232:164–168

    Google Scholar 

  12. 12.

    Zhuang H, Srikanth V, Jiang X, Aronov I, Wenclawiak BW, Luo J, Ihmels H (2010) Elucidation of Different Steps Involved in Allylamine Functionalization of the Diamond Surface and Its Polymerization by Time-of-Flight Secondary Ion Mass Spectrometry. Chem Mater 22:4414–4418

    Google Scholar 

  13. 13.

    Hutton LA, Newton ME, Unwin PR, Macpherson J (2011) Factors Controlling Stripping Voltammetry of Lead at Polycrystalline Boron Doped Diamond Electrodes: New Insights from High-Resolution Microscopy. Anal Chem 83:735–745

    Google Scholar 

  14. 14.

    Wachholz F, Duwensee H, Schmidt R, Zwanzig M, Gimsa J, Fiedler S, Flechsig GU (2009) Template-free galvanic nanostructuring of gold electrodes for sensitive electrochemical biosensors. Electroanalysis 21:2153–2159

    Google Scholar 

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Acknowledgments

The authors are grateful for the financial support (DFG Heisenberg fellowship FL 384/7-2).

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Correspondence to Gerd-Uwe Flechsig.

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ESM 1

Supporting information is available online: Fig. S1 displaying calibration plots and LODs measured by DP-stripping voltammetry at −0.5 V deposition potential in the range from 0 to 1,000 ppb Cu. (DOC 339 kb)

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Hafez, A.M., Koch, U. & Flechsig, G. ToF-secondary ion mass-spectrometric study of copper deposition and stripping on directly heated screen-printed gold electrodes. J Solid State Electrochem 17, 1563–1570 (2013). https://doi.org/10.1007/s10008-013-2083-6

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Keywords

  • Heated gold electrode
  • Stripping voltammetry
  • Potentiometry
  • Copper
  • Time of Flight, ToF
  • Secondary ion mass spectrometry, SIMS