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Nano Structured and Photoelectrochemical Systems for Solar Photon Conversion, 2008, p

Nano Structured and Photoelectrochemical Systems for Solar Photon Conversion, 2008, p

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Nano Structured and Photoelectrochemical Systems for Solar Photon Conversion, 2008
Nano Structured and Photoelectrochemical Systems for Solar Photon Conversion, 2008

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12.2.1 Single- frequency admittance measurements (Mott–Schottky plots)

Solid-state semiconductor junctions are commonly characterised by AC and DC

electrical techniques. In the case of Schottky barrier (metal/semiconductor) devices,

single admittance measurements (‘CV measurements’) are often used to determine

the space-charge layer capacitance Cscl as a function of applied voltage bias V.

Analysis of the potential dependence of Cscl provides values of the barrier height and

doping density. This method has been applied widely in semiconductor

electrochemistry to determine flatband potentials and doping densities (Morrison,

1980). The semiconductor may be in contact with either a redox electrolyte or an inert

supporting electrolyte. In the first case, the analogy with the metal/semiconductor

junction is exact. The redox potential defines the Fermi energy (work function) of the

contact, and hence the equilibrium barrier height. In the absence of redox species, the

contact is essentially blocking, and the band bending is controlled by the externally

applied voltage (ideally polarisable case).

Under depletion conditions, the withdrawal of majority carriers from the inter-

facial region of the semiconductor/electrolyte junction creates a space-charge layer

consisting of ionised donors (for n-type semiconductors) or acceptors (for p-type

semiconductors). The dependence of the space-charge density Qscl on the potential

Experimental Techniques in Photoelectrochemistry

677

difference ∆φscl across the space-charge region defines the differential space-charge

capacitance Cscl = ∂ Qscl / ∆φscl. If the doping density is less than 1018

cm–3

, and

provided that no charge is stored in defects (surface states) at the semiconductor

surface, changes in applied potential appear almost entirely across the space-charge

region. Consequently, the potential drop in the Helmholtz layer at the interface

remains almost constant. In this situation, ∆φscl is equal to U – Ufb, where U is the

electrode potential (vs. a suitable reference electrode) and Ufb is the flatband potential.

The capacitance under depletion and accumulation conditions is obtained by solving

the Poisson–Boltzmann equation (details may be found in, for example, Morrison,

1980). Only the depletion case is considered here. The potential dependence of Cscl is

described by the Mott–Schottky equation (given here for an n-type semiconductor)

fb

2

D

o

scl

1

2

kT

UU

C

qN

q

=

− −

ε ε

(12.1)

where ND is the donor density and ε εo is the permittivity of the semiconductor. Mott–

Schottky plots of 1/2

scl

C vs. U are used to obtain doping densities and flatband pot-

entials. Since Cscl is a potential-dependent differential capacitance, it must be

measured using small-amplitude AC methods.

The ideal semiconductor/electrolyte interface forms a blocking junction under

reverse-bias conditions, so the reverse-bias current density iDk is small and independ-

ent of voltage. For large-bandgap materials, reverse-bias currents are usually higher

than predicted because surface defects allow some interfacial electron transfer to

occur. The small-amplitude electrical behaviour of the junction is therefore

represented by a parallel combination of the space-charge capacitance Cscl and a

resistance defined by Rp = U/ iDk. The finite resistances of the ohmic contact and

the solution also affect the AC response. These resistances are lumped into a single

series resistance Rs to give the equivalent circuit shown in Fig. 12.1. Note that the

Helmholtz capacitance CH does not appear in the figure since in most cases Cscl is

much smaller than CH (unless the semiconductor is highly doped), so that CH (which

Figure 12.1 Simplest small-signal equivalent circuit representing the semiconductor/electrolyte junction

under depletion conditions. Rs = total series resistance, Rp = parallel resistance due to charge transfer,

Cscl = space-charge layer capacitance.

R

s

Rp

Cscl

Cscl

Rs

Rp

L. M. Peter and H. Tributsch

678

appears in series with Cscl) can be neglected. A note of caution is appropriate here. If

CH is included for the case of highly-doped semiconductors, the inequality Cscl << CH

is no longer valid, and the DC potential distribution must be obtained by solving the

Poisson–Boltzmann equation with appropriate boundary conditions (Morrison, 1980).

If Rs is small and the applied electrical AC frequency f is chosen such that Rp is

much greater than 1/2π f Cscl, the impedance Z of the junction is dominated by Cscl, i.e.

Z 1/jω Cscl, where ω = f. Under these conditions, the admittance Y = 1/Z = jω

Cscl. The magnitude of the admittance is therefore a linear function of Cscl, and its

phase is +90o

. If Rp is comparable with 1/ω Cscl (as is often the case at high

frequencies), the out-of-phase (90o

) component of the admittance is still given by jω

Cscl, and the in-phase (0o

) component is equal to Rp

–1

. This approximation has been

widely used as the basis for single-frequency measurements of Cscl as a function of

potential, using the set-up shown in Fig. 12.2. A small-amplitude (≤10 mV) sinusoidal

AC voltage is superimposed on the DC potential applied to the sample by the

potentiostat. Since the AC current depends linearly on the admittance, the out-of-

phase signal measured by the lock-in amplifier is a linear function of Cscl. The phase

and sensitivity of the measurement system can set using a set of calibrated

capacitances in the appropriate range. The calibration should be repeated for each

frequency.

There are two main sources of error in this type of measurement. The first arises

from the failure of the approximation Y jω Cscl if the sample has a poor ohmic

contact or the frequency is too high. If this is the case, the out-of-phase component is

no longer a linear function of Cscl. The error, which usually manifests itself as an

unexpected frequency dependence of Cscl, can be avoided by making frequency-

dependent impedance measurements with a frequency response analyser (as discussed

in Section 12.2.2). The other source of errors arises from the frequency response of

Figure 12.2 Experimental arrangement for single-frequency admittance (capacitance) measurements.

secondary

reference

working

lock-in

amplifier

potentiostat

ramp generator

sine generator

recorder

cell

Experimental Techniques in Photoelectrochemistry

679

the potentiostat circuit. In general, the AC voltage applied to the electrode is not

identical with the signal used to programme the potentiostat. Its magnitude and phase

are changed as a result of attenuation arising from the frequency response character-

istics of the potentiostat circuit (including the electrochemical cell). The voltage

output from the current-measuring amplifier is also attenuated and phase-shifted. The

higher the measurement frequency, the more acute these problems become.

The simplest way around these problems is to set up the system with a calibrated

capacitance box and a small (<10 ohm) series resistance to ensure potentiostat

stability. The in-phase response is set accurately to zero by adjusting the phase control

on the lock-in. The magnitude of the out-of-phase (90o

) response is then calibrated

over the range of interest using the capacitance box. The current amplifier should be

set to a low sensitivity range to enhance the frequency response of the system: the

output from the potentiostat to the lock-in should ideally be only a few millivolts, so

that the current amplifier is operating in its small-signal regime.

Often the slopes and intercepts of Mott–Schottky plots are not independent of

frequency, calling into question the validity of the simple approach outlined above.

The simplest reasons for non-ideal Mott–Schottky plots are instrumental error or

incorrect assumptions about the equivalent circuit. However, these plots are often not

linear even in the absence of these artefacts. Physical explanations of non-linearity

include non-uniform doping, surface roughness, surface states and deep donor or

acceptor levels (Bonham and Orazem, 1992). In the case of thin semiconductor films,

Mott–Schottky plots may reach a plateau at large values of U – Ufb, when the space

charge extends throughout the film and Cscl tends towards the geometric capacitance

Cgeo = dε εo, where d is the film thickness (Özsan et al., 1996). Figure 12.3 illustrates

this behaviour. The transition voltage VTR can be used to find the film thickness.

Frequency dispersion can arise from dielectric relaxation, surface roughness,

carrier trapping in the space-charge region and relaxation of deep donor/acceptor

levels (Oskam et al., 1991). One of the commonest causes of non-ideality in

semiconductor/electrolyte junctions is the presence of states at the surface that can

exchange electrons with the solid and liquid phases. These are referred to by the

general term ‘surface states’, adopted from solid-state physics, but in most cases their

structural and chemical identity is obscure. Even for a perfect solid/vacuum interface,

termination of the lattice leads to energy states that lie in the bandgap, and surface

reconstruction is common. Solid/liquid interfaces are more complex since atoms in

the solid can form bonds with species from the solvent or electrolyte. This termination

does not necessarily lead to surface states. In the case of silicon in fluoride media, for

example, the surface is terminated by hydrogen atoms and the density of surface states

is very low (Oskam et al., 1996a, 1996b, 1996c; Hoffmann et al., 1998). Oxide-

L. M. Peter and H. Tributsch

680

covered silicon surfaces, by contrast, are usually less ideal owing to the presence of

sub-stoichiometric silicon compounds.

In an ideal semiconductor/electrolyte junction, the space charge in the semi-

conductor is balanced by the counter-charge in the electrical double layer formed in

the electrolyte. Since the Helmholtz capacitance CH is generally much larger than Cscl,

most of the potential drop is located in the semiconductor. The surface ionic charge

on the semiconductor is determined by the acid/base or ion-exchange properties of the

surface. Oxide electrodes usually exhibit a Nernstian pH dependence of the flatband

potential as a consequence of the change in surface dipole. However, high densities of

electronic surface states can effectively ‘metallise’ the semiconductor surface. The

surface charge then varies with applied potential in such a way that a significant

fraction of the change in total potential difference appears across the Helmholtz

double layer rather than across the space-charge region of the semiconductor. This

effect is referred to as ‘Fermi-level pinning’ (Gilman et al., 1993; Lewerenz, 1993;

Hutton et al., 1994). The surface states responsible for this effect may arise from

crystal imperfections and surface damage, or they may be formed as a consequence of

surface reactions, either in the dark or under illumination (Peter et al., 1997). The

effect of Fermi level pinning is manifest as a flat region in Mott–Schottky plots

arising from the almost constant value of the total capacitance.

Figure 12.3 Mott–Schottky plot for a thin (80 nm) film of n-CdS on tin oxide-coated conducting glass,

showing the transition from Mott–Schottky behaviour to the geometric capacitance limit when the space-

charge region extends to the substrate. Electrolyte 0.1 mol dm–3

Na2S, pH 13. Adapted from Özsan et al.

(1996).

Experimental Techniques in Photoelectrochemistry

681

A special case of non-ideal Mott–Schottky behaviour arises if impurity atoms such

as hydrogen diffuse into the near-surface region of the sample: this has been observed

for p-GaP (Li et al., 1984) and p-Si (Mandal et al., 1990), where hydrogen atoms can

act as ‘near-surface’ states, or compensate the doping, leading to an insulating surface

region or even to conversion from p-type to n-type. This leads to large shifts in the

apparent flatband potential.

12.2.2 Electrochemical impedance spectroscopy (EIS)

Many of the problems of interpretation that arise from single-frequency admittance

measurements can be avoided if frequency-resolved measurements are made (Gomes

and Vanmaekelbergh, 1996; Macdonald et al., 1998). These can be carried out with a

programmable lock-in amplifier or using a frequency response analyser (FRA) with

its associated electrochemical interface. FRA systems are optimised to overcome the

problems associated with attenuation and phase shift. The current to the cell is

measured using a series resistance and a wide-bandwidth voltage amplifier, and the

AC voltage appearing across the cell between the working and reference electrodes is

measured directly to avoid errors arising from the performance of the potentiostat

control amplifier. Provided that adequate care is taken, measurements can be extended

into the MHz region.

In three-electrode measurements, the main source of error at high frequencies is

the reference electrode. It is advisable to use a low-impedance reference electrode or a

quasi-reference electrode such as an annealed Pt wire when making EIS measure-

ments above 100 kHz. Lead lengths should be kept to a minimum to minimise stray

inductance and capacitance, and the cell design should be optimised to minimise

series resistance losses: glass frits used to separate the counter-electrode compartment

are a common source of high-frequency artefacts, and these should be avoided.

FRA systems are versatile, and they can be controlled to acquire and analyse the

data required to construct Mott–Schottky plots, for example. Unfortunately, the ease

of use of FRA-fitting software can lead to errors of interpretation that arise from a

failure to relate fitting elements to the physical system. Several equivalent circuits

may give the same frequency-dependent impedance response. No a priori distinction

between degenerate circuits is possible. It is necessary to study the system response as

a function of additional experimental variables (DC voltage, concentration, mass

transport conditions etc.) in order to establish whether the circuit elements are related

in a predictable way to a model of the physical system.

L. M. Peter and H. Tributsch

682

EIS has been used to study the kinetics of outer-sphere redox reactions at

semiconductors in the dark (Meier et al., 1997; Meier et al., 1999). The reactions

involve majority carriers (electrons for n-type materials), and the electrode behaves

like a metal with a low and potential-dependent electron density. The EIS response

can be modelled by the equivalent circuit shown in Fig. 12.1, where Rp is interpreted

as the faradaic resistance obtained by linearising the potential dependence of the

current associated with electron transfer to the redox species.

EIS has also been used to study the dissolution of p-type silicon in fluoride media

(Ozanam et al., 1992; Bailes et al., 1998). The system is interesting because the

current–voltage curve exhibits a region of negative slope in the electro-polishing

region, as shown in Fig. 12.4. Figure 12.5 shows examples of the impedance

response. The high-frequency capacitance is associated with the presence of an oxide

layer on the silicon. The low-frequency semicircle arises from the dissolution process.

It can have a negative low-frequency intercept because Rp is the inverse of the slope

of the steady-state current–voltage characteristic, which can be positive or negative.

The parallel capacitance in this case is not Cscl, but a pseudocapacitance associated

with the growth and dissolution of the surface oxide.

EIS measurements can also be carried out under conditions where illumination of

the semiconductor generates a photocurrent. The technique is then referred to as

photoelectrochemical impedance spectroscopy, PEIS. Interpretation of the results in

terms of passive RC circuit elements is no longer appropriate since the system

contains a current source. A more satisfactory approach is to relate the impedance

response directly to the physical processes responsible for the photocurrent

(Ponomarev and Peter, 1995; Peter, 1999; Peter and Vanmaekelbergh, 1999).

Figure 12.4 Steady-state current–voltage curve for p-Si (100) in 0.1 mol dm–3

NH4F, pH 3. Note the

change in slope from positive to negative at around 1.5 V. Adapted from Bailes et al. (1998).

U vs. SCE / V

i / m

A cm

–2

Experimental Techniques in Photoelectrochemistry

683

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