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Using the MottSchottky Equation

K. Gelderman, L. Lee, and S. W. Donne*

Discipline of Chemistry, University of Newcastle, Callaghan, NSW 2308, Australia; *scott.donne@newcastle.edu.au

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 energy. With the current movement away from fossil fuel-based

energy towards more environmentally friendly, renewable energy sources, research in this area is again gaining momentum. 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 inherent 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

one of the fundamental properties of any semiconductorelectrolyte 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 semiconductorelectrolyte interface, together with the

MottSchottky equation for determining the flat-band potential.

Of primary importance in the development of electrochemical photovoltaic cells is understanding the relationship

between semiconductor and electrolyte energy levels (25).

An energy-level diagram for both an n-type semiconductor

and a redox couple in an electrolyte solution is shown in Figure 1A. For the semiconductor we have identified the valenceand 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 semiconductor potential, , changing as e 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 solution; that is,

(1)

Ox + e

Red

The energies of the solution states depend on whether the

state is occupied (Red) or vacant (Ox), owing to the different solvent-sheath energies, , around the Red and Ox species. Since solvent molecule exchange between the

coordination sphere of the redox-active species and the bulk

electrolyte is a dynamic process leading to a range of solventsheath energies, the density of redox states is best described

in terms of separate Gaussian distributions (Figure 1A). The

redox Fermi level, EF(redox), is again the energy at which the

probability of a state being occupied by an electron is 0.5.

www.JCE.DivCHED.org

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

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 semiconductor 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 depletion in the semiconductor will change depending on the applied 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 .

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):

Under the circumstances shown in Figure 1A, that is,

where EF > EF(redox), the MottSchottky 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

semiconductorelectrolyte interface. For the complete derivation the reader is referred to the Supplemental MaterialW

for this experiment. However, in short, the starting point for

the derivation is Poissons equation in one dimension that

describes the relationship between charge density and potential difference, , in a phase,

d2

dx

(2)

(4a)

I (t ) = I 0 + I m sin ( t + )

(4b)

Z ( ) =

V (t )

I (t )

(4c)

current flowing through the electrode, respectively, when the

impedance experiment is conducted, Vm and Im are the maximum voltage and current of the supplied sinusoidal signal,

respectively, and is the phase angle of the resultant current. An alternative, more convenient description is to express Z() in terms of orthogonal axes rather than polar

coordinates:

away from the semiconductor surface, is the dielectric constant of the semiconductor, and 0 is the permittivity of free

space. Using the Boltzmann distribution to describe the distribution of electrons in the space charge region and Gauss

law relating the electric field through the interface to the

charge contained within that region, Poissons equation can

be solved to give the MottSchottky equation:

k T

1

2

V Vf b B

=

2

2

e

C

0 A e ND

(3)

686

V (t ) = V0 + Vm sin ( t )

Z ( ) = Z + j Z

(5a)

Z = Z ( ) cos ()

(5b)

Z = Z ( ) sin ()

(5c)

Z ( ) =

Vm

Im

www.JCE.DivCHED.org

(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

K3[Fe(CN)6] (+0.8 V versus SCE).

High-temperature oven capable of at least 1200 C

Equipment to carry out EIS; e.g., gain-phase analyzer

(Solartron 1253), potentiostat (Princeton Applied Research EG&G 273A), controlling software (ZPlot by

Schlumberger)

Figure 4. Modified Randles circuit used to model the ZnO electrode interface. Terms are defined in the text.

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

A typical EIS result is shown in Figure 3. The first notable 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 processes 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[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 transfer 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 element (CPE) to take into account any non-homogeneity

of the ZnO surface; for example, surface roughness. Surface non-homogeneity is indicated by the depressed semi-

www.JCE.DivCHED.org

circuit, ZCPE, is

Z CPE = m cos

m

2

j sin

m

2

(6)

= 2f ), 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 parallel 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 component 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.

MottSchottky Plot

To establish a MottSchottky plot as described above,

the interfacial capacitance, C, can be determined directly from

(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

687

In the Laboratory

is comparable to previously reported values (6 1024 m3;

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

(1 M KCl).

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

of 0.57 0.02 with no apparent trend in the data. Therefore, assuming that the electrode capacitance can be represented directly by 1, a MottSchottky plot was constructed

(Figure 5). According to eq 3, the flat-band potential of ZnO

was 0.316 0.033 V versus SCE in 7 104 M K3[Fe(CN)6]

(1 M KCl). The steps apparent in Figure 5 most likely originate from the equivalent circuit fitting procedure applied to

data with some low frequency noise (Figure 3). The resultant values when squared then tend to vary only slightly, as

seen in the MottSchottky plot.

In comparison with previous works, Freund and

Morrison (9) reported 0.41 V versus SCE for a similar system. 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 conductivity differences along different crystallographic planes.

To determine ND from the MottSchottky equation

(slope in Figure 5), Morrison (2) has quoted the use of a dielectric constant of 8.5 for this system. Therefore, from the

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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