A Novel Cell For In-Situ

SE/EQCM
By Young group
Cell Schematic
• The base of the cell is the working
electrode connected to a QCM
controller
• The body consists of two electrode
ports, two ports for quartz rod
‘windows’, and two ports for
solvent flow through (not used in
this work)
• Solvent is added in a sealable
opening in the center of the cell
body
Solvent Refraction Effect
45 In air
In solution
140 • The solvent can cause a slight
40
phase shift (∆) in s and p

Delta (D)
Psi (Y )

120
35
polarized waves while the
30
100 amplitude (Ψ) is unaffected in all
Bare Crystal
25 measurements
1.5 2.0 2.5 3.0 3.5

Energy (eV) • Note that the phase shift is not

44
42 In air 120 always present; this could be the
40
In solution Delta (D)
result of differences in light
Psi (Y )

38
36
100
intensity measurement samples
34
32 80
due to cell alignment
Crystal + PANI Film
30
1.5 2.0 2.5 3.0 3.5

Energy (eV)
 Deposition Methods and Results
• PANI was deposited on QC’s from a 0.1
50
6 M aniline solution with 1 M sulfuric
40 acid supporting electrolyte

Thickness (nm)
• Five successive 1.5s duration pulses at
D m (mg/cm2)

4 Mass 30
0.8 V (vs. SSC) were applied at the WE
20 before collecting an SE measurement
Thickness
2
10
• Thickness was calculated using either a
Lorentz or Gaussian model with a fixed
0 0 oscillation at ~1.5 eV
• Note that densities (1.1-1.7 g cm-3)
0 10 20 30 40 agree well accepted lit. value of 1.3 g
Growth Cycle cm-3
 Cyclic Voltammetry
0.2
0.5 V
• Newly deposited films were
Forward Sweep 0.4 V cycled between -0.2 and 0.8 V
0.1 0.2 V
0.3 V 0.6 V (vs. SSC) at 20 mV s-1 in pH 2
0.1 V sulfuric acid
I (mA)

0.0 V

0.0 0.2 V
0.6 V
• The first anodic peak is
0.0 V 0.1 V
0.3 V 0.5 V associated with protonation of
the PANI film and is reduced due
-0.1 Reverse Sweep
to the low acid concentration
0.4 V

-0.2 0.0 0.2 0.4 0.6 0.8

Ewe vs. SSC (V)
 Film Electrochromism
0.60
0.55 Forward Sweep • The changes in optical properties
0.50 0.5 V with potential agree well with
0.45
0.40
UV-VIS data from previous
0.35 0.6 V reviewed literature
0.30 0.4 V
• The shift in the absorption band
k

0.25 0.3 V
0.20 0.2 V at 0.6 V is unexpected at this
0.15 0.1 V
0.10 0.0 V
potential; it is possible that this
0.05 transition of the spectrum to
0.00 higher energies occurs at lower
300 400 500 600 700 800 potentials in dilute acid
Wavelength (nm)
Molecular Changes during CV
0.55
• As expected, the quinoid imine band
0.50
0.45
(~700 nm) increases in strength as
0.40 700 nm potential is increased to 0.5 V
0.35 • As previously stated, the decrease at
0.30 0.6 V is unexpected and could be a pH
k

0.25 dependent effect or caused by inter-

0.20
chain radical combinations
0.15
0.10 • The band at 435 nm is associated with
0.05 435 nm
radical amine cations; the increase at
0.00 0.6 V could be from increased
0.0 0.1 0.2 0.3 0.4 0.5 0.6 protonation of the film or band
Ewe vs. SSC (V) overlap from the spectrum shift
Charge Transfer Resistance
40 • Resistance was modeled using an
equivalent circuit of a three
Forward Sweep
resistor/two phase element circuit
Rct (W x 103)

30 connected in series
Reverse Sweep
• Conductivity reaches a maximum
at 0.4 V
20
• Resistance doesn’t vary much over
the potential range; perhaps if the
10 range was expanded order of
0.0 0.1 0.2 0.3 0.4 0.5 0.6 magnitude changes would occur
E vs. SSC (V)
 Film Loss Under and Oxidizing Potential
110 • PANI film was held at 1.0 V for 1-
105
100 current 5 min durations, followed by a
Percent Change (%)

95 SE/EIS/CV measurement
90
85
80 mass • Film density measurements vary
75 from 1.6-2.1 g cm-3 over the
70
65 experiment time
60
55 thickness • Current reduction was measured
50
45 from the maximum of the first
40 anodic peak in the CV
35
0 20 40 60 80 100 120
time (min)
Absorption Strength Reduction
1.6
• The band positions in the
1.4 measured range don’t change
1.2
time with time under a constant
1.0 potential
0.8 • However, they do decrease in
k

0.6
intensity as film material is lost
0.4
0.2 • EIS data shows interesting
0.0 changes in film resistivity
300 400 500 600 700
Wavelength (nm)
 Absorption Strength Under a Reducing
Potential
• A PANI film was held at -0.2 V for 1 to 5
min intervals
• After each hold, EIS and CV
0.05
measurements were taken
• The figure shows a reduction in the
k

quinoid imine band as the film is

progressively reduced to the
benzenoid form
• The first few cycles show substantial
0.00

300 400 500 600 700

thickness change that quickly stabilizes
Wavelength (nm)
and remains relatively constant
throughout
Soon to be released!
• Mass, thickness, resistance, and current changes from the reduction
experiment
• Resistance data from the oxidation experiment