Probe fabrication and characterisation

1 Quartz theta capillaries are pulled to a fne point

(typically 50 nm 1 m) using a laser pipette puller
2 One barrel is flled with pyrolytic carbon to form a solid electrode
3 The carbon electrode is modifed if desired
www.npl.co.uk
Advancing SECM-SICM for
the study of electrocatalysis
at nanostructured interfaces
Michael A. OConnell,
*
Joshua Lewis and Andrew J. Wain
National Physical Laboratory, Hampton Road Teddington Middlesex TW11 0LW, UK
*mike.o-connell@npl.co.uk
Acknowledgments
This work was funded by the National Measurement System in the
Department for Business Innovation and Skills (UK).
Introduction
Scanning electrochemical microscopy (SECM) allows the wealth of information
that can be gleaned from analytical electrochemistry to be mapped on a local
scale. Modern refnements to the technique have increased the resolution of
measurements and allowed deconvolution of topography from activity.
In this poster we demonstrate one such technique, scanning electrochemical
scanning ion conductance microscopy (SECM-SICM), for the study of
nanostructured surfaces.
Scanning electrochemical-scanning ion
conductance microscopy (SECM-SICM)
Tip-sample distance control via
migration current measurement
Positional feedback via current
measurement from solution
no extra hardware required
Dual function capillary probes
Channel 1 - solution-flled pipette
Channel 2 solid electrode
Laser pulling generates intrinsically
small capillary apertures
(50 nm to 1m typically)
Electrodes can be made in the
range of a few tens of nanometers
to a few microns.
Probes can be approximately sized
by performing cyclic voltammetry.
Shown here is a tip of <100 nm in
1 mM FcMeOH.
Heat
Dual
Capillary
Butane
Argon
Gold nanodisk imaging
The SICM provides
faithful topographical
imaging shown here
on a model platinum
microband electrode
array. A range of
electrochemical
modes are accessible
shown here are
feedback and
substrate generation
tip collection
images using
1 mM FcMeOH.
The carbon tip is modifed by
electrodeposition of platinum to enhance
the oxygen reduction signal (black cv bare
C tip, red cv with Pt)
The platinum nanosphere (100 200 nm)
substrate is formed by a pulsed growth
electrodeposition technique to give a
monodisperse array.

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Conclusions
Combined topographical and electrochemical imaging has been demonstrated with resolution of less than 100 nm
Carbon tips have been modifed with platinum to allow detection of dissolved oxygen
Combined imaging has been demonstrated on a single particle level
Small tips (<100 nm) can be used to image smaller structures. Here 150 nm gold disks on silicon are
imaged in feedback mode demonstrating the impressive resolution. The SICM topography is clearly
deconvoluted from the electrochemical signal. An atomic force microscopy (AFM) image of the
sample demonstrates the faithfulness of the image.
Platinum band
model system
Approach curves to the glass, unbiased band and generator band
show the current response (SECM in red, SICM in black)
Oxygen reduction
at platinum catalyst
nanospheres
Oxygen reduction at individual platinum catalyst
nanospheres is imaged using a competitive reduction mode.