In the Laboratory

Flat-Band Potential of a Semiconductor: W

Using the Mott–Schottky Equation
K. Gelderman, L. Lee, and S. W. Donne*
Discipline of Chemistry, University of Newcastle, Callaghan, NSW 2308, Australia; *scott.donne@newcastle.edu.au

It has long been known that metals are good conductors A

of electricity. However, the discovery of semiconductors and
the transistor effect by Bardeen, Shockley, and Brattain in 1948
(summarized in ref 1) generated considerable interest in the
electronic properties of all materials and paved the way for
the development of the myriad of electronic devices we have
today. Of particular relevance to this article are photovoltaic
cells, which can be used to convert light into electrical en-
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ergy. With the current movement away from fossil fuel-based

energy towards more environmentally friendly, renewable en-
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ergy sources, research in this area is again gaining momen-

tum. Previously, it was at a peak during the “energy crisis” of
the early 1980s, when there was a global deficiency of fossil
fuels. At the present time, however, the motivation is the in-
herent realization that fossils fuels are a finite resource, as well
as being detrimental to the environment when combusted.
In this article we describe an experiment to determine B
one of the fundamental properties of any semiconductor–elec-
trolyte system; namely, its flat-band potential. To gain a more
thorough understanding of this semiconductor property,
which will be of significance to both senior undergraduate
and graduate students, we begin by describing the nature of
the semiconductor–electrolyte interface, together with the
Mott–Schottky equation for determining the flat-band po-
tential.

The Semiconductor–Electrolyte Interface

Of primary importance in the development of electro-
chemical photovoltaic cells is understanding the relationship
between semiconductor and electrolyte energy levels (2–5).
An energy-level diagram for both an n-type semiconductor
and a redox couple in an electrolyte solution is shown in Fig- C
ure 1A. For the semiconductor we have identified the valence-
and conduction-band edges (VB and CB, respectively), the
band-gap energy (EG), and the Fermi level (EF), which is the
energy at which the probability of an electronic state being
occupied is 0.5. These bands are dependent on the semicon-
ductor potential, φ, changing as ᎑eφ where e is the charge on
an electron.
The energy levels for redox-active species in solution arise
by virtue of the donors (Red) and acceptors (Ox) in solu-
tion; that is,
Ox + e− Red (1)
The energies of the solution states depend on whether the
state is occupied (Red) or vacant (Ox), owing to the differ-
ent solvent-sheath energies, λ, around the Red and Ox spe-
cies. Since solvent molecule exchange between the
Figure 1. (A) Schematic of an n-type semiconductor showing the va-
coordination sphere of the redox-active species and the bulk
lence and conduction bands (VB and CB, respectively), Fermi level
electrolyte is a dynamic process leading to a range of solvent- (EF), band-gap energy (EG), and the redox states in solution (Ox and
sheath energies, the density of redox states is best described Red), with their corresponding Fermi level (EF(redox)) and solvent-reor-
in terms of separate Gaussian distributions (Figure 1A). The ganization energy (λ). (B) Electronic equilibrium between the n-type
redox Fermi level, EF(redox), is again the energy at which the semiconductor and redox couple in solution. (C) Situation when the
probability of a state being occupied by an electron is 0.5. semiconductor is at its flat-band potential Vfb.

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 In the Laboratory
Figure 2. Schematic of the assembled electrode.
When an n-type semiconductor and a redox couple come
into contact, where EF is higher in energy compared to
EF(redox), equilibrium can be achieved through the transfer of
electrons from the semiconductor to Ox so that the Fermi
levels for both phases are equal, as in Figure 1B. This has the
effect of charging the semiconductor positively, and since
semiconductor carrier densities are much lower than those
in solution, the diffuse charge in the semiconductor (space
charge region) is counterbalanced essentially by a sheet of
charge in the electrolyte. Changing the voltage of the semi-
conductor artificially through the use of a potentiostat causes
the semiconductor and redox couple Fermi levels to separate,
and hence the level of band bending owing to electron deple-
tion in the semiconductor will change depending on the ap-
plied voltage. When the applied voltage is such that there is
no band bending, or charge depletion (Figure 1C), then the
semiconductor is at its flat-band potential, Vfb .
The Mott–Schottky Equation
Under the circumstances shown in Figure 1A, that is,
where EF > EF(redox), the Mott–Schottky equation can be used
to determine the flat-band potential of the semiconductor.
Understanding its derivation is essential for this experiment
because it reinforces many key concepts associated with the
semiconductor–electrolyte interface. For the complete deri-
vation the reader is referred to the Supplemental MaterialW
for this experiment. However, in short, the starting point for
the derivation is Poisson’s equation in one dimension that
describes the relationship between charge density and poten-
tial difference, φ, in a phase,
d2 φ ρ rent. An alternative, more convenient description is to ex-
2
= − (2)
dx ε ε0
where ρ corresponds to the charge density at a position x
away from the semiconductor surface, ε is the dielectric con-
stant of the semiconductor, and ε0 is the permittivity of free
space. Using the Boltzmann distribution to describe the dis-
tribution of electrons in the space charge region and Gauss’
law relating the electric field through the interface to the
charge contained within that region, Poisson’s equation can
be solved to give the Mott–Schottky equation:
1 2 k T
2
= 2
V − Vf b − B
C ε ε 0 A e ND e (3)
686 Journal of Chemical Education • Vol. 84 No. 4 April 2007
Here C and A are the interfacial capacitance and area, re-
spectively, ND the number of donors, V the applied voltage,
kB is Boltzmann’s constant, T the absolute temperature, and
e is the electronic charge. Therefore, a plot of 1兾C 2 against
V should yield a straight line from which Vfb can be deter-
mined from the intercept on the V axis. The value of ND can
also be conveniently found from the slope knowing ε 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 en-
capsulated, 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 solu-
tion of 7 × 10᎑4 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 de-
gassed 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(ω), can be determined using
Ohm’s law (5):
V (t ) = V0 + Vm sin (ω t ) (4a)
I (t ) = I 0 + I m sin (ω t + θ) (4b)
V (t )
Z (ω ) = (4c)
I (t )
Here V0 and I0 are the dc bias potential and the steady-state
current flowing through the electrode, respectively, when the
impedance experiment is conducted, Vm and Im are the maxi-
mum voltage and current of the supplied sinusoidal signal,
respectively, and θ is the phase angle of the resultant cur-
press Z(ω) in terms of orthogonal axes rather than polar
coordinates:
Z (ω ) = Z ′ + j Z ′′ (5a)
Z ′ = Z (ω ) cos (θ) (5b)
Z ′′ = Z (ω ) sin (θ) (5c)
Vm
Z (ω ) = (5d)
Im
• www.JCE.DivCHED.org
 In the Laboratory

Here j is the imaginary number ( j = √᎑1). A range of fre-

quencies, ω, can be examined to generate an impedance spec-
trum.
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 with-
out the need for manual input.
Figure 3. Typical EIS response for ZnO immersed in 7 × 10᎑4 M
K3[Fe(CN)6] (+0.8 V versus SCE).
Specialized Equipment

• Pellet press and hydraulic ram

• High-temperature oven capable of at least 1200 ⬚C
• Equipment to carry out EIS; e.g., gain-phase analyzer
(Solartron 1253), potentiostat (Princeton Applied Re-
search EG&G 273A), controlling software (ZPlot by
Schlumberger)
Figure 4. Modified Randles circuit used to model the ZnO elec-
Hazards trode interface. Terms are defined in the text.

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 experi-
ment. Both the Ag-epoxy and chemically resistant epoxy can
be hazardous if in contact with the skin. In terms of tech-
niques, using a high-temperature furnace can be a consider-
able hazard. Any user should wear appropriate personal
protective equipment such as a face mask, lab coat, and ther-
mally insulating gloves, as well as use long tongs when plac-
ing in or extracting samples from the furnace. When using
electrochemical apparatus, the user should always ensure cor-
rect electrical contacts between the equipment and cell. Fur-
thermore, equipment compliance should be evaluated using
a dummy cell.
Results and Discussion
EIS Data and Analysis
A typical EIS result is shown in Figure 3. The first no-
table feature is the depressed semicircular response to changes
in frequency. Interpretation of the EIS data was carried out
by considering the possible faradaic and non-faradaic pro-
cesses that can occur at the ZnO surface and then relating
those back to a modified Randles circuit (6).
The only possible faradaic process involves charge
transfer in the [Fe(CN)6]3−兾[Fe(CN)6]4− redox couple. This
is probably one of the more well-defined and reversible
redox couples and so is ideal for this study. Charge trans-
fer in this redox couple is represented by a resistance (RCT)
in the Randles circuit (Figure 4). In parallel with RCT is
the non-faradaic electrode capacitance caused by the build
up of charge at the ZnO electrode surface. In the Randles
circuit we have represented this by a constant-phase ele-
ment (CPE) to take into account any non-homogeneity
of the ZnO surface; for example, surface roughness. Sur-
face non-homogeneity is indicated by the depressed semi-
circle seen in Figure 3. The impedance of a CPE in an ac
circuit, ZCPE, is
mπ mπ
Z CPE = σ ω−m cos − j sin (6)
2 2
where σ is the CPE prefactor, ω is the angular frequency (ω
= 2πf ), m is the CPE exponent (0 ≤ m ≤ 1), and j is the
imaginary number ( j = √᎑1). Note that if m = 1 then ZCPE
represents an ideal capacitor, ZC. RCT and ZCPE are in paral-
lel with each other because they represent alternate charge
paths at the electrode surface. Also included in series with
RCT is a Warburg impedance, ZW, which takes into account
diffusion of electroactive species towards the electrode, which
is most significant at low frequencies. ZW is essentially the
same as ZCPE, but with m = 0.5 in eq 6. The final compo-
nent is another resistance (RS) representing the voltage drop
in the electrolyte owing to the passage of current between
the surface of the ZnO electrode and the reference electrode.
EIS data collected in this work were then modeled by
complex nonlinear least-squares regression (7, 8) using the
total impedance of the modified Randles circuit (Figure 4).
From the extracted parameters, the interfacial capacitance was
determined.
Mott–Schottky Plot
To establish a Mott–Schottky plot as described above,
the interfacial capacitance, C, can be determined directly from
σ (eq 6) if m = 1. However, m was substantially less than
unity over the entire voltage range considered owing most
probably to surface non-homogeneity. Nevertheless, m was

www.JCE.DivCHED.org • Vol. 84 No. 4 April 2007 • Journal of Chemical Education 687

 In the Laboratory
Figure 5. Mott–Schottky plot for ZnO in 7 × 10᎑4 M K3[Fe(CN)6]
(1 M KCl).
constant over the entire voltage range, having an average value
of 0.57 ± 0.02 with no apparent trend in the data. There-
fore, assuming that the electrode capacitance can be repre-
sented directly by 1兾σ, a Mott–Schottky plot was constructed
(Figure 5). According to eq 3, the flat-band potential of ZnO
was ᎑0.316 ± 0.033 V versus SCE in 7 × 10᎑4 M K3[Fe(CN)6]
(1 M KCl). The steps apparent in Figure 5 most likely origi-
nate from the equivalent circuit fitting procedure applied to
data with some low frequency noise (Figure 3). The result-
ant σ values when squared then tend to vary only slightly, as
seen in the Mott–Schottky plot.
In comparison with previous works, Freund and
Morrison (9) reported ᎑0.41 V versus SCE for a similar sys-
tem. However, in this example a single crystal of ZnO was
used, allowing for a well-defined crystal plane, [001], to be
exposed to the electrolyte. The polycrystalline ZnO electrode
used here means that many crystal planes would be exposed,
suggesting that the different Vfb values arise as a result of con-
ductivity differences along different crystallographic planes.
To determine ND from the Mott–Schottky equation
(slope in Figure 5), Morrison (2) has quoted the use of a di-
electric constant of 8.5 for this system. Therefore, from the
688 Journal of Chemical Education • Vol. 84 No. 4 April 2007
slope of the Mott–Schottky plot, ND = 2 × 1024 m᎑3, which
is comparable to previously reported values (6 × 1024 m᎑3;
ref 2 ). The deviation is most probably due to the action of
surface states in the polycrystalline electrode capturing and
immobilizing the carriers.
Summary and Conclusions
In this experiment, suitable for fourth-year under-
graduate and graduate students, we have explored the na-
ture of semiconductor materials through determination of
the flat-band potential using the Mott–Schottky 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 semicon-
ductor electrodes. Electrochemical impedance spectroscopy
was then employed to examine the semiconductor–elec-
trolyte, 7 × 10᎑4 M K3[Fe(CN)6] (1 M KCl), interface as
a function of applied voltage. To achieve this a modified
Randle’s circuit was developed to interpret the impedance
data, from which a value for the interfacial capacitance
was determined. A Mott–Schottky plot was then con-
structed that allowed a flat-band potential of ᎑0.316 ±
0.033 V versus SCE to be determined. The number of car-
riers, ND, was also determined: ND = 2 × 1024 m᎑3. Both
results were comparable to literature data emphasizing the
soundness of the technique.
W
Supplemental Material
Instructions for the students, including pre- and post-
lab 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, 98–1, 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. O’M.; Reddy, A. K. N. Modern Electrochemistry:
Plenum Press: New York, 1970; Vols. 1 and 2.
5. Impedance Spectroscopy: Emphasizing Solid Materials and Sys-
tems; 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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