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Figure 1. (A) Schematic of an n-type semiconductor showing the valence and conduction bands (VB and CB, respectively), Fermi level
(EF), band-gap energy (EG), and the redox states in solution (Ox and
Red), with their corresponding Fermi level (EF(redox)) and solvent-reorganization energy (). (B) Electronic equilibrium between the n-type
semiconductor and redox couple in solution. (C) Situation when the
semiconductor is at its flat-band potential Vfb.
685
In the Laboratory
Here C and A are the interfacial capacitance and area, respectively, ND the number of donors, V the applied voltage,
kB is Boltzmanns constant, T the absolute temperature, and
e is the electronic charge. Therefore, a plot of 1C 2 against
V should yield a straight line from which Vfb can be determined from the intercept on the V axis. The value of ND can
also be conveniently found from the slope knowing and A.
Experimental
Electrode Preparation
A schematic of the semiconductor electrode used in this
work is shown in Figure 2. Essentially a compacted, sintered
disk of polycrystalline ZnO was mounted using chemically
resistant epoxy into a polypropylene tube. Before being encapsulated, a contact wire was attached to the back of the
ZnO disk using Ag-loaded epoxy. The surface of the ZnO
was polished, thoroughly washed with ultra-pure water, and
then patted dry prior to use.
Electrochemical Protocol
The ZnO electrode was immersed in an aqueous solution of 7 104 M K3[Fe(CN)6] in 1 M KCl, together with
a saturated calomel reference electrode (SCE) and a Pt counter
electrode. Previously the electrolyte solution had been degassed of oxygen by purging with nitrogen.
The basis of an electrochemical impedance spectroscopy
(EIS) experiment is to apply a small amplitude sinusoidal ac
voltage, V(t), and then measure the amplitude and phase angle
(relative to the applied voltage) of the resulting current, I(t).
From this the impedance, Z(), can be determined using
Ohms law (5):
(2)
(4a)
I (t ) = I 0 + I m sin ( t + )
(4b)
Z ( ) =
V (t )
I (t )
(4c)
686
V (t ) = V0 + Vm sin ( t )
Z ( ) = Z + j Z
(5a)
Z = Z ( ) cos ()
(5b)
Z = Z ( ) sin ()
(5c)
Z ( ) =
Vm
Im
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(5d)
In the Laboratory
Here j is the imaginary number ( j = 1). A range of frequencies, , can be examined to generate an impedance spectrum.
In this experiment, the impedance of the ZnO electrode
was measured at bias potentials ranging from +0.8 to 0.5 V
(versus SCE) in 50-mV increments, with 15 minutes allowed
for equilibration at each new potential. The frequency range
was from 20 kHz to 0.1 Hz, with Vm set at 5 mV. Clearly
this is a long experiment and so it is highly preferable to use
an automated system that can control the experiment without the need for manual input.
Specialized Equipment
Hazards
K3[Fe(CN)6] is toxic if swallowed or by skin contact;
however, the quantities used in this experiment are small.
ZnO and KCl do not pose a serious hazard in this experiment. Both the Ag-epoxy and chemically resistant epoxy can
be hazardous if in contact with the skin. In terms of techniques, using a high-temperature furnace can be a considerable hazard. Any user should wear appropriate personal
protective equipment such as a face mask, lab coat, and thermally insulating gloves, as well as use long tongs when placing in or extracting samples from the furnace. When using
electrochemical apparatus, the user should always ensure correct electrical contacts between the equipment and cell. Furthermore, equipment compliance should be evaluated using
a dummy cell.
Results and Discussion
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m
2
j sin
m
2
(6)
687
In the Laboratory
In this experiment, suitable for fourth-year undergraduate and graduate students, we have explored the nature of semiconductor materials through determination of
the flat-band potential using the MottSchottky equation.
Experimentally, a technique was developed for preparing
a suitable polycrystalline ZnO electrode for study. Note
that a similar approach could be used for other semiconductor electrodes. Electrochemical impedance spectroscopy
was then employed to examine the semiconductorelectrolyte, 7 104 M K3[Fe(CN)6] (1 M KCl), interface as
a function of applied voltage. To achieve this a modified
Randles circuit was developed to interpret the impedance
data, from which a value for the interfacial capacitance
was determined. A MottSchottky plot was then constructed that allowed a flat-band potential of 0.316
0.033 V versus SCE to be determined. The number of carriers, ND, was also determined: ND = 2 1024 m3. Both
results were comparable to literature data emphasizing the
soundness of the technique.
W
688
Supplemental Material
Instructions for the students, including pre- and postlab questions and the complete derivation of the Mott
Schottky equation, and notes for the instructor are available
in this issue of JCE Online.
Literature Cited
1. Shockley, W. B. Proc. Electrochem. Soc. 1998, 981, 26.
2. Morrison, S. R. Electrochemistry at Semiconductor and Oxidized
Metal Electrodes; Plenum Press: New York, 1980.
3. West, A. R. Solid State Chemistry and Its Applications; John
Wiley and Sons: Chichester, United Kingdom, 1984.
4. Bockris, J. OM.; Reddy, A. K. N. Modern Electrochemistry:
Plenum Press: New York, 1970; Vols. 1 and 2.
5. Impedance Spectroscopy: Emphasizing Solid Materials and Systems; Macdonald, J. R., Ed.; John Wiley and Sons: New York,
1987.
6. Randles, J. E. B. Discuss. Faraday Soc. 1947, 1, 11.
7. Boukamp, B. A. Solid State Ionics 1986, 18, 136.
8. Boukamp, B. A. Solid State Ionics 1986, 20, 30.
9. Freund, T.; Morrison, S. R. Surface Science 1968, 9, 119.
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