FAST SCAN CYCLIC VOLTAMMETRY SIMULATION

FOR SILICON NANOELECTRODES

Marioara Avram, Anca Angelescu, Irina Kleps, Mihaela Miu, Alina Popescu
National Institute for Research and Development in Microtechnologies (IMT),
P.O.Box 38-160, Bucharest, Romania,
fax: 40.1.4908238, tel.: 40.1.4908412/33. e-mail:marioaraa@imt.ro
Abstract.-A program based on four procedures,
written in Borland-Pascal was applied
for the
simulations of fast scan cyclic voltammetry using as
working electrode a metaVsilicon pyramidal
nanostructure array. The model for the electrode
process includes diffusion (Ficks law), electrode
kinetics (Butler-Volmer equation), and chemical
reaction kinetics.

consists of both, the chemical and electrical

energy associated with bringing an electron to
the electrode.
i = f(E) curves are usually obtained with a
measuring system including a pulse generator, a
potentiostat, and a recording unit, and the
electrochemical cell with three electrodes:
working, reference and counter electrode(Fig. 1).

I. INTRODUCTION
Cyclic voltammetry (CV) is a potentialcontrolled
reversible
electrochemical
experiment. As applications there are: (i) the
analysis of the electrochemical reaction
mechanisms, and (ii) the liquid media toxic
metallic traces detection. It also provides the
experimentalist
with
a simulation-based
approach for the analysis of cyclic
voltammogrames.

+
1

POTENTIAL

POTENTIOSTAT

A cyclic potential sweep is applied on an

electrode and the current response is observed.
Analysis of the current response can give
information about:
- the thermodynamics and kinetics and
mechanism of solution chemical reactions
initiated by the heterogeneous electron transfer,
at the electrode / solution interface;
- the amount of metallic impurities in liquid
media.

N2

Fig.l. CV measuring system.

The simulations done in this paper are helpful in

the preliminary stages of a cyclic voltammetry
study, and the CV graphics are intended for
comparison of experimental and simulated data.

In our CV simulations we have taken into

account as working electrode an array of
pyramidal Si nanostructures or of disk
microstructures, covered with either gold or
platinum [ 11. The main advantages of these type
of electrodes used in the CV experiments are: (i)
high detecting resistive media; (ii) the mass
transport rate to the micro- or nano-electrode is
higher than that can be achieved using
macroelectrodes; (iii) the signal-to-background

11. THE CYCLIC VOLTAMMETRIY

METHOD
In the CV experiments an oxidation and
reduction of a solution chemical species at the
electrode, take place. The electrode potential E
0-7803-6666-2/01/$10.00 0 2001 IEEE
43

ratio is higher, so the detection limits are lower;

(iv) signal-to-noise ratios are improved, since
the noise levels depend on the active area of the
electrodes, whereas the signal depends on the
total area of the diffusion field.

mathematical treatment of CV measurements

many procedures are necessary.
The electrochemical kinetics is described by the
Butler-Volmer equation that links the variables
for current, potential and concentrrations and
chemical reaction kinetics:

111. THEORETICAL BACKGROUND

Many laws describe the effects due to the
potential applied to the system and redox
current. The applied potential E controls both
the concentrations of the redox species at the
electrode surface COand the reaction rate k", as
described by Nernst or Butler-Volmer equations
respectively. The Nernst equation is:

k", is the rate of the reaction and expresses the

flux of electrons at the electrode surface
(cm/sec);
a, the cathode transfer coefficient, reflects the
nature of the transition state;
(1 - a)= p, anodic transfer coefficient;
A, is the electrode area; C, concentrations
given in moledmilliliter (M xlO-').
A program based on 4 procedures, written in
Borland-Pascal [2] have been used to simulate
the cyclic voltammetric measurements, taken
into account as working electrode a
nanoelectrode
(metal/silicon
pyramidal
nanostructured arrays).
The mass transport to the nanoeletrode is
dominated by radial diffusion while the
convective mass transport contribution is less
significant. The calculations are based on typical
experimental parameters, as input data: the
applied potential limits, the scan rate, the
chemical reaction constant and the reaction rate.
All these parameters corespond to a real
situation, and the simulated CV curves are
intended for comparison of experimental and
simulated data.
The procedures are:
1. Set-up procedure. Input all the initial
conditions, experimental parameters, and
electrochemical mechanisms.
2. Electrode procedure. It was calculated the
flux due to electron transfer at the electrode,
according to the Butler-Volmer equation.
3. Diffusion procedure. It was calculate the
diffusion of each species according to the
Fick's law, and the concentrations were
modified in each spatial element.
4. Reaction procedure. It contains the
calculation of the extent of reaction for all
species and the modification accordingly to
the concentrations calculated earlier in the
diffusion procedure.

where:

E" is the potential of the reaction versus

the standard hydrogen electrode, with all species
at unit activity;
E = electrode potential;
R =gas constant 8.3144 J / (mol K);
T = absolute temperature;
n = electrons number;
F = Faraday number, 96485 C / echiv,
k h e m = chemical reaction constant;
v scan rate, V/cm.
The relation (1) could be written:

Cr and COare the concentrations of oxidised and

reduced metals, on the electrode surface.
If the diffusion is important, the resulting
current (faradaic current) is related by Fick's
law, to the material flux at the electrode/solution
interface :
CD = - ADO(CCO/ CT x),
(3)
where:
Do is the diffusion coefficient of the
oxidised species, and
x, the distance related to the electrode
surface.
A similar equation may be written also, for the
reduced species.
The electrode reaction, diffusion and chemical
reaction are three interdependent components of
the electrochemical mechanism and for the

44

Simulated cyclic voltanimograms are presented

in Fig. 2 - Fig.7.

Eo10.371; kon0.00q; kchem-50; v=lOOcdsec; E C l V

IV. DISCUSSION
For the computer simulation of CV experiments,
the following process parameters were varied:
The anodic and cathode potential limits, E;
and E, values (Fig. 2, Fig. 3 ) .
The cyclic linear potential sweep applied on the
electrode is described by its initial (E;),
switching (Es), final (Ef) potentials, and sweep
rate (v, in V/sec) /3/. The potential as a function
of time is
E = El vt in forward and reverse sweep.
In our simulations we have limited the potential
area at 5V.
The anodic potential limit was 2,5V. A greater
value determines an initial oxidation current,
which leads to the oxidation products adsorption
on the electrode surface, and as a result, the
voltaniinograme
peaks
will
increase
irreproducible. So, this value is selected to avoid
any charge transfer.
The cathode potential limit was -2,W. Greater
values lead to the reduction of the electrolyte
support, and metals are deposited on the
electrode surface, the other measurements will
be affected.
Scan rate v, and the measuring time t, are
related by t = RT/ F v (Fig. 5).
The measuring time is determined by the signal
frequency and it must be greater than the
chemical reaction time (10 -3 sec). So, all
chemical changes are studied.
E" the potential of the reaction versus the
standard hydrogen electrode (Fig. 4),
k" the rate equation for heterogeneous
electron transfer (Fig.6),
hl,e,,,
chemical reaction constant (Fig.7).

1,o

1,s

0.2

0.0

4.2

4.4

90

-1,o

-0,s

rntentid (v)

Fig.3. Simulated graphs for different Es values

ko=O.OOl: kchem=50: v=lOOcm/sec: Ei=O.BV: E s = 4 S V

1,0

0,s

0,6

42

0,O

0,2

0,4

Eo=1.32vl

44

46

WmIid 0
Fig. 4. Simulated graphs for different Eo values.

-.-

_,,,,,;

7".

v=SOdSX

--'--v=5OoCldSX;

0.4

35

1,O

4.6

wmkd (v)

Fig. 2. Simulated graphs for different Ei values.

0,8

0,6

0,4

92

b
'

.*

0,O
FwenGd (v)

42

44

Fig. 5. Simulated graphs for different scan rate values.

45

46

Eo

3 0,244V;

kchem

for low scan rate (100V/sec), and low potential

E0=0,244V.
The same effect obtained for a series of
increasing solution chemical rate constants at
constant scan rate (Fig. 7) would be observed
with a constant chemical rate constant and
decreasing scan rate.
The variation of initial and final potential limits
leads to sigmoid CV curves, displaced on the
potential axes (Fig. 2, Fig. 3 ) .
The heterogeneous constant variation k, (Fig. 6)
determines CV curves with different rate of
reversibility. High k, values (k, < 0,l) are
characteristic for reversible processes, and lower
values (k, =0,001- 0,0001) for irreversible ones.
Regarding the chemical reaction constants kchem,
(Fig. 7), for higher values, the CV curve peak is
shifted in the positive direction. This effect is
due to the activation of the reaction (the reaction
rate is increased), as a result of the redox species
moving (Nernst equation). The same effect is
obtained by a lower scan rate at a determined
kchemvalue.

50; Ei i: 1V; Es - O S & v =IO0 cmlsec

-2,ox 10-5

-4,Ox10-5
1,O

0,8

0,6

0,4

0.2
0,O
Potential (V)

-0,2

-0,4

-0,6

Fig. 6: Simulated graphs for different k , values.

Eo = 0.371; ko

0.001; v = 1000cmlsec; Ei = l&Es = 4.5V

2,5x10-JI
2,OxlO-4

l i e

V. CONCLUSIONS

A program based on 4 procedures, written in

Borland-Pascal have been used to simulate the
cyclic voltammetric measurements, taken into
account as working electrode a nanoelectrode
(metal/silicon pyramidal nanostructured arrays).
The calculations are based on typical
experimental parameters, as input data: the
applied potential limits, the scan rate, the
chemical reaction constant and the reaction rate.
All these parameters corespond to a real
situation, the simulations done in this paper are
helpful in the preliminary stages of a cyclic
voltammetry study, and the CV graphics are
intended for comparison of experimental and
simulated data.

Fig. 7. Simulated graphs for two khem

values.

The ratio of cathode to anode peak current is a

function of chemical rate constant and scan rate
(Fig. 5 , Fig. 6).
The simulated curves obtained for different scan
rate values (Fig.5) present differences. The
transition to the stationary state is achieved by
reducing the scan rate. At hi@ scan rate,
1000-10000 mVlsec, the CV are wave-shaped;
as the scan rate is lower, 1-10 mV/sec, the CVbecomes sigmoidal, as a result of particular
shape of the difi'usion field and the high
diffusive mass transport rate, characteristic for
nanoelectrodes. The same CV curve is obtained

REFERENCES
[I] Irina Kleps, Anca AngeIescu, Roxana Vasilco,
and Dan Dascalu, Biomedical Microdevices

3:1, pp. 27-31, 2001.

[2] David K.Gosser. Jr, Cyclic Voltammetry, 1994.
[3] G.T.Kovacs, C.W.Storment, SKounaves, Sensors
and Actuators, B 23, pp. 41-47, 1995.

46