The emergence
of organic–inorganic
metal halide perovskites as active components in solar cells has sparked
a great interest in the scientific community. A steep rise was witnessed
in the power conversion efficiencies, which currently peaks at a certified
value of 22.7%.
1
The attractiveness of
these materials resides in their exceptional defect tolerance,
2,3
tunable light absorption and emission properties,
4,5
enhanced
charge carrier transport and lifetime,
4
and cost-effective preparation and processability.
6
Applications beyond solar cells have also been studied,
in light emitting diodes,
7,8
lasers,
8
photodetectors,
9,10
X-ray detectors,
11
γ-detectors,
12
and smart windows.
13
Several research
groups have focused on the synthesis of new organic
hole-transporting materials (HTMs) for perovskite solar cells (PSCs).
14−16
An emerging class of HTMs is the family of organic polymers, which
inherently possesses higher hole mobility than dopant-free small molecules.
16
Interestingly, this growing interest has not
been accompanied by the growth in the arsenal of deposition techniques.
To date, spin-coating remains the preferred choice to deposit such
hole conducting polymer films.
In a n–i–p PSC design, hole conducting
layers, mainly consisting of polymeric materials (e.g., P3HT
17−19
and PTAA
19
) that are soluble in perovskite
antisolvents are studied. Although it was demonstrated that PEDOT
accepts holes as effectively as spiro-OMeTAD,
20
its use apart from a few examples,
21−23
has been restricted
to inverted SC designs (p–i–n junction).
The direct spin-coating of the aqueous PEDOT:PSS solution is not a
good option because it is known to degrade the perovskite layer. The
inverted designs, however, pose further challenges such as overcoming
the energy mismatch between FTO/PEDOT and attaining adequate surface
coverage of the perovskite layer, which is determined by the morphology
of the underlying PEDOT.
Scheme 1
Illustration of the Assembly and Operation of the Perovskite Solar
Cell with PEDOT Hole-Transporter
Although electrochemical deposition of the HTM layer has
shown
promising results in the case of dye-sensitized solar cells,
24
it remained an elusive task for the n–i–p PSC architecture up to this point. This
is mainly because of the instability of MAPbI3 in polar
solvents,
25
in which most electrochemical
syntheses are carried out. Further complications arise from the dynamic
exchange between the cations and halide ions in the perovskite layer
and those present in the electrolyte. Such an exchange of ions can
significantly alter the composition of the perovskite layer.
26
It has been demonstrated recently that the electrochemical
properties of MAPbI3
27−29
and related materials
30−34
can be studied in dichloromethane based electrolytes. Special care
must be exercised while conducting electrodeposition, because an external
electrochemical bias can induce unintended side reactions (e.g., corrosion
of the perovskite layer).
29
However, by
implementing carefully controlled conditions, one can employ electrodeposition
as a technique and utilize its superior control over several efficiency-determining
factors (e.g., morphology, regularity, conductivity, optical absorption,
and layer thickness).
24
In this study,
we report the electrochemical deposition of PEDOT
(HTM layer) directly on the MAPbI3 film deposited on a
FTO/TiO2 electrode and its implementation in a perovskite
solar cell (PSC) with an n–i–p architecture
(Scheme 1
). The effect
of electrochemical post-treatments of the HTM layer on the performance
of PSC has also been scrutinized.
Results and Discussion
Electropolymerization
of Hole-Transport Layer
The first
step was to ensure that the MAPbI3 layer remains intact
during the electropolymerization. FTO/TiO2/MAPbI3 electrodes with a thin MAPbI3 layer
were fabricated to
monitor the optical changes during electrochemical deposition of the
HTM layer, as described in the Supporting Information. The time frame of the experiment
and potential-range of the PEDOT
electrodeposition (in the absence of bis-EDOT monomer) was established
through prolonged immersion of the FTO/TiO2/MAPbI3 electrode in the solvent and carrying
out cyclic voltammetric experiments.
As established in our earlier methods and protocol work,
29
0.1 M Bu4NPF6 in dichloromethane
offers the best electrochemical condition as no significant change
in the overall shape of the optical absorption of the perovskite film
is observed after 10 min of exposure (Figure S1A). As for the electrochemical properties,
MAPbI3 layers
were more resistant to oxidation than reduction (Figure S1B). Top-down and cross-sectional
SEM images as well
as XPS studies confirmed the stability of the FTO/TiO2/MAPbI3 electrodes during both
immersion in the electrolyte and oxidative
biasing, up to 1.1 V (Figures S2 and S3). However, EDOT cannot be used as the polymerization
precursor, because its polymerization (oxidation) potential would
exceed the electrochemical stability of MAPbI3 layers.
To overcome this limitation, we employed bis-EDOT as a precursor (Scheme S1). The
use of bis-EDOT, in turn, allowed
us to carry out the (oxidative) electropolymerization and produce
PEDOT films without degrading the MAPbI3 layer.
35
The electropolymerization process initiated
by the electrochemical oxidation of bis-EDOT on FTO/TiO2/MAPbI3 electrodes was monitored
using in situ spectroelectrochemical experiments (Figure 1
A–C). The gradual growth of PEDOT
during potentiodynamic deposition was evident from the change in absorption
as well as the increasing (pseudo)capacitive current in the potential
range of 0.0–0.6 V. The absorption peak at 450 nm was attributed
to EDOT oligomers and the broad absorption in the 500–800 nm
region (Figure 1
B)
was assigned to the polymer product, viz., PEDOT layer. To correlate
the polymer formation with the oxidation of bis-EDOT, the current
density of the first polymerization half cycle was plotted along with
the absorbance increase at 700 nm (Figure 1
C). A sharp rise in the current at 0.7 V
was accompanied by the absorbance increase at 700 nm, thus confirming
the polymerization of bis-EDOT.
Figure 1
(A) Potentiodynamic deposition of PEDOT
with 25 mV s–1 sweep rate in a 0.01 M bis-EDOT,
0.1 M Bu4NPF6 DCM on a PSC architecture (FTO/bl-TiO2/mp-TiO2/MAPbI3) employing a thin
MAPbI3 layer. (B)
UV–vis absorbance spectra recorded after each cycle at E = 0.0 V during polymerization.
(C) First half-cycle of
the potentiodynamic deposition plotted together with the absorbance
change at 700 nm. (D) Potentiostatic deposition of PEDOT at different
potentials in a 0.01 M bis-EDOT, 0.1 M Bu4NPF6 DCM solution on a PSC architecture
employing regular thickness MAPbI3 layers with a polymerization charge density of
10 mC cm–2. (E) UV–vis absorbance spectra of PSCs after
PEDOT electrodeposition at E = 0.9 V for different
polymerization charge densities. (F) Absorbance change of the PSCs
compared to a HTM-free cell by varying the polymerization charge density
at different applied potentials.
Although polymerization starts at 0.7 V, prolonged exposure
to
the electrolyte needs to be avoided. As shown in Figure 1
D, adequate polymerization
rate was achieved at potentials above 0.9 V. In addition, by varying
the electrochemical charge density, the thickness of the formed PEDOT
layer can be fine-tuned, as deduced from the absorbance spectra (Figure 1
E,F). The UV–vis
absorption features did not indicate any noticeable changes corresponding
to perovskite layer absorption, thereby confirming the conservation
of original MAPbI3 architecture during the electropolymerization
process.
Characterization of PEDOT Layer
SEM images captured
the morphological features of the PEDOT layers on the MAPbI3 film following the deposition
of PEDOT at 1.0 V with Q
pol = 5 mC cm–2. The top-view images
show that the electropolymerized layer of PEDOT completely covers
the MAPbI3 layer (Figure 2
A). The smooth MAPbI3 surface was not visible
anymore, instead a furry polymer coating developed. These images confirmed
the homogeneity of the PEDOT layer and that the MAPbI3 remained
intact during the electrodeposition. In order to determine the thickness
of the formed PEDOT, cross-sectional FIB-SEM images were recorded
(Figure 2
B). The measured
PEDOT thickness was compared with the value, calculated from the charge
density employed during polymerization (Figure 2
C). These values fall in the range of the
HTM thicknesses (40–300 nm) employed in the case of MAPbI3 PSCs using PEDOT.
21,22
Raman-spectroscopic
studies (Figure 2
D)
further confirmed the characteristics of an electrochemically deposited
PEDOT on top of the MAPbI3 layer.
Figure 2
(A) Top-view SEM image
before (upper part) and after PEDOT (lower
part) electrodeposition and (B) cross-sectional FIB-SEM image of a
PSC, where the PEDOT electrodeposition was carried out at E = 1.0 V with Q
pol = 5 mC cm–2. (C) Theoretical and actual PEDOT layer thicknesses
(determined from cross-sectional SEM images). (D) Raman-spectra of
a fully assembled FTO/TiO2/MAPbI3/PEDOT architecture
and a FTO/PEDOT reference material.
Post-treatment of PEDOT Layer
The doping level of the
HTL is important for optimization of PSCs. When we evaluated the photovoltaic
performance of the MAPbI3 PSCs employing the electrochemically
deposited PEDOT hole-transporting layers, without any post-treatment
(see Supporting Information for detailed
analysis (Figure S4)), all of them exhibited
low open circuit voltage (V
OC) (Figure 3
A) and fill factor
(FF). The inability of PEDOT layer to transport the holes efficiently
results in increased charge recombination (Figure
S4). One way to overcome these issues is to modulate the doping
level of PEDOT layer. We employed electrochemical post-treatment approach
to alter the doping level (Scheme S2).
PEDOT films deposited at 1.0 V, with a Q
pol = 3–10 mC cm–2 seemed to be optimal to
evaluate post-treatment conditions. This reductive post-treatment
method, however, had an unintended side-effect, as revealed by cross-sectional
SEM images (Figure S5A,B). Though the reduction
of PEDOT is beneficial for its performance, it destroys some of the
MAPbI3 from the underlying layer. Three different strategies
were employed to mitigate this effect: (i) rapid reduction at −0.6
V for 10 s (Figure S6A); (ii) mild reduction
at −0.5 V for 60 s (Figure S6B);
and (iii) rapid-mild reduction at −0.5 V for 20 s (Figure S6C).
Figure 3
(A) Effect of PEDOT thickness (polymerization
charge density) on
the open circuit voltage in a FTO/TiO2/MAPbI3/PEDOT PSC for PEDOT layers electrodeposited
at E = 1.0 V. (B) Chronoamperometric curves recorded for the PEDOT layers
electrodeposited at E = 1.0 V, when a reductive post-treatment
at E = −0.6 V was employed. (C) Buildup of
the open circuit potential in a FTO/TiO2/MAPbI3/PEDOT SC for the PEDOT layers electrodeposited
at E = 1.0 V for Q
pol = 10 mC cm–2. (D) J–V curve of the champion
device containing a PEDOT layer electrodeposited at E = 1.0 V for Q
pol = 10 mC cm–2, where the postreduction step was at E = −0.6
V for t = 10 s.
There was an improvement in the V
OC of the devices compared to the untreated PEDOT in all cases (Figure S7), but the
J
SC and the FF remained low in most cases (Figure
S9A–D). The only exception was the rapid reduction,
where the champion cell had a 5.9% efficiency (
Figure 3
D). Top-down and
cross-sectional SEM images recorded for samples post-treated with
the rapid reduction revealed that the degradation of the MAPbI3 layers can be avoided
using this strategy (Figure S8).
Transient Absorption Measurements
To probe the hole
accepting ability of PEDOT, transient absorption spectroscopic measurements
were carried out (Figure 4
A). The characteristics of the spectra are in good accordance
with MAPbI3 spectra in the literature.
36
The most prominent feature, the ground state bleach at
760 nm, is caused by charge separation due to band edge transition
in MAPbI3.
36
Furthermore, there
is no additional bleaching signal present at ∼500 nm that would
arise from PbI2 in the material. The recovery of the 760
nm bleach follows second-order kinetics (Figure 4
B). Fitting the data to a biexponential decay
reveals that the average lifetime (see Supporting
Information for the calculations and detailed analysis) has
the following trend: reduced PEDOT (t
weighed avg = 1280 ps) < as-is PEDOT (t
weighed avg = 1660 ps) < no HTM (t
weighed avg = 1750 ps). The shorter lifetime indicates the transfer of photogenerated
holes from MAPbI3 layer to PEDOT layer. Furthermore, the
postsynthetic reduction technique improves the hole accepting properties
of the PEDOT film.
Figure 4
(A) Time-resolved transient spectra of an FTO/TiO2/MAPbI3/PEDOT PSC employing a thin
MAPbI3 layer recorded
following 387 nm laser pulse excitation. The PEDOT layer was prepared
and post-treated just as the champion device. (B) Bleaching recovery
profiles at 760 nm of different FTO/TiO2/MAPbI3/PEDOT PSCs.
Conclusions
The
electrochemical deposition of PEDOT offers a convenient way
to deposit a hole-transport layer on a MAPbI3 layer for
designing n–i–p junction perovskite
solar cells. By employing potentiostatically controlled electrodeposition
technique, it is possible to obtain controlled thicknesses of HTM
layers. An electrochemical postreduction step introduced to control
the doping level of the as-deposited PEDOT films is an essential step
in achieving better performance of PSCs. Care should be exercised
not to destroy the underlying MAPbI3 layer during the post-treatment
process. The champion device showed a power conversion efficiency
of 5.9%. The results presented in this study open new opportunities
to employ electrochemistry to assemble complex architectures of optically
active perovskites.