Ways to Measure Flatband Potential

Putting a semiconducting electrode in contact with a solution containing a well-defined redox couple Start a Vfb, immerse semiconductor in solution with Eredox positive of Vfb:
EC

EF
EV
Vrdx Vrdx

 Now we illuminate the equilibrated semiconductor: Holes are scavenged by the reduced species in the redox couple Electrons accumulate in conduction band, forcing EF to rise. EC
EF
+
Vrdx
The difference between the electrode potential in the dark and the potential in the light is less than or equal to the difference between Vfb and Vredox Can measure Vfb if Vredox known

EV

For very intense illumination, photopotential approximates voltage difference between Vrdx and Vfb Recombination causes the photopotential to not reach Vfb

Can measure photovoltage

For a variety of solution redox couples, and determine the polarity Extrapolate to flatband potential

nc,s is a function of applied potential - the more positive the potential applied to the semiconductor the fewer electrons at the surface, so that the cathodic current gets smaller with positive bias:

J = JCexp[-q(V-Vfb)/kT] - JA
Eox Eredox

Eredox Ered

Measurement of Vfb
Making a Mott-Schottky plot The space charge layer - along with the Helmholtz layer and the diffuse layer in solution - are planes of charge separated by a distance and thus have capacitance (C = q/V) For capacitors in series:
1 1 1 1 = + + ... CT C1 C2 C3
So largest capacitance contributes least to the 1/CT term!

Equivalent Circuit
Space Charge Layer = SC Helmholtz Layer = H Diffuse Layer = D

H EC
SC +
EV
D

Resistances to electron motion ALSO - so can construct a model of charge distribution at the semiconductor-liquid interface using capacitors and resistors

Mott-Schottky
Diffuse Layer: Lots of charge in response to fairly small potentials = large capacitance. Helmholtz Layer: Also quite a bit of charge for a given potential difference between solution and surface, C = 10 to 100 F/cm2 So - space charge layer capacitance is usually the smallest in salt solutions to that 1/C is large

Mott-Schottky Equation
+ -

L 0 CL = dL
" 2 0 V V fb W =$ $ qN d # % ' ' &
1/2

Width of SC layer is function of voltage, so as voltage approaches Vfb the width goes down so that the capacitance goes up.

Mott Schottky Equation

# 2 &# 1 kT & =% (% V V fb ( 2 CSC $ qN d 0 '$ q'

CSC at its highest when (V-Vfb)-(kT/q) is at a minimum. At is 298K, the kT/q correction is minor (~25 mV) so that 1/Csc2 is minimal when the applied potential is equal to the flatband potential.

How to measure CSC?

Equivalent circuit modeling

Impedance Spectroscopy
V=IR (Ohms law) Or E= IR (Electrochemical impedance spectroscopy, EIS)

Ohms law okay for DC

Ideal resistor follows Ohms law Resistance independent of frequency AC current and voltage signals are in phase with each other.

In AC systems, however, things are a bit more complex and ideal resistors are hard to find...

EIS:
Apply a DC electrochemical potential Modulate the DC potential with a small AC signal:
Apply small AC modulation

Apply DC

Monitor how output current responds

http://www.gamry.com/App_Notes/EIS_Primer/EIS_Primer.htm

Current Response
Current is also sinusoidal, but phase shifted:

1/sec Radians/sec

 Current output will be:

Impedance, Z, is defined similarly to resistance but includes the time function:

The impedance is thus a function of a magnitude Z0 and a phase shift

Lissajous Figure:
Leftover from the days of oscilloscopes which can still be very useful!

Eulers relation again

The impedance Z has a real part and an imaginary part. That is, it can be factored into Z0cos and Z0jsin. These separate values can be plotted

Nyquist Plot:
Both axes generally given in Ohms -ImZ

=0 RealZ

Impedance Spectroscopy The Basics:

Apply AC modulation and measure current response Characterizes AC resistance and capacitance behavior, which can be modeled through equivalent circuits

Adapted from (Bisquert 2004)

Equivalent Circuits
RSS CSS CSS CSC Rf CH Ru

RSS CSC RU