Materials for Renewable and Sustainable Energy (2019) 8:3

https://doi.org/10.1007/s40243-018-0139-3

ORIGINAL PAPER

An approach to optimize pre‑annealing aging and anneal conditions

to improve photovoltaic performance of perovskite solar cells
Dahiru M. Sanni1,2 · Yuanqing Chen3 · Aditya S. Yerramilli3 · Esidor Ntsoenzok4,5 · Joseph Asare1,6 ·
Sharafadeen A. Adeniji1 · Omolara V. Oyelade1 · Adebayo A. Fashina1 · T. L. Alford3,5 

Received: 10 August 2018 / Accepted: 10 December 2018 / Published online: 19 December 2018
© The Author(s) 2018

Abstract
In this study, we reported a low-temperature, one-step solution process to fabricate perovskite solar cells using dehydrated
lead acetate as the lead source. These perovskite films were aged at 200 s before thermal annealing at 90 °C for 5 min.
Uniform perovskite films with lesser pinholes were obtained by this technique. The inverted planar (n-i-p) perovskite solar
cell device resulted in a power conversion efficiency of 13%. A substantial finding was that the devices demonstrated high
reproducibility. We also investigated the effect of annealing temperature on the optical and structural properties of the films
and on the photovoltaic performances of the fabricated solar cell devices. For the aforementioned, a low-temperature, one-
step solution process, the optimal temperature was achieved at 90 °C.

Keywords  Dehydrated lead acetate · Aging time · Perovskite solar cells

Introduction the perovskite materials (e.g., as the tunable bandgap, direct

bandgap, large optical absorption coefficient, high charge
The organic–inorganic halide perovskite solar cells have carrier mobilities, low exciton binding energy, and cost-
continued to attract serious research interest since the first effective solution processable [1–4]). Different structures of
introduction as solar light by Miyasaka and co-workers with perovskite solar cells have been investigated and reported
a power conversion efficiency (PCE) of 3.8% in 2009 to over extensively in recent years which include perovskite sensi-
22%. This outcome is due to the tremendous advantages of tized solar cells [5, 6], mesoscopic perovskite solar cells [1,
2, 7] and planar heterojunction perovskite solar cells [8–10].
The simplest structure of all these devices is the planar het-
Electronic supplementary material  The online version of this erojunction perovskite solar cells; this is because they are
article (https​://doi.org/10.1007/s4024​3-018-0139-3) contains low-temperature processed as compared to mesoporous
supplementary material, which is available to authorized users.
layers which are high-temperature processed [11]. A great
* T. L. Alford research interest has been devoted to the inverted planar het-
TA@asu.edu erojunction perovskite solar cells (p-i-n) architecture as a
significant type of perovskite solar cells. Besides their very
1
Department of Theoretical and Applied Physics, African low hysteresis when compared to the n-i-p planar hetero-
University of Science and Technology, Abuja, Nigeria
junction devices [12], the p-i-n structure can also be pro-
2
Department of Physics, Federal University Dutsin-Ma, duced by a low-temperature solution process employing
Dutsin‑Ma, Katsina State, Nigeria
poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid)
3
School for Engineering of Matter, Transport and Energy, (PEDOT:PSS) films for the hole transport layers, which is
Arizona State University, Tempe, AZ 85287, USA
compatible with flexible substrates for flexible solar cell
4
CEMHTI-CNRS Site Cyclotron, 3A rue de la férollerie, applications [13].
45071 Orléans, France
Different techniques have been employed for the prepa-
5
Department of Material Science and Engineering, African ration of perovskite films, including vapor deposition [13],
University of Science and Technology, Abuja, Nigeria
vapor-assisted solution process [14], solution process via
6
Physics Department, Faculty of Computing and Applied one-step [1, 15] and two-step sequential deposition [16].
Sciences, Baze University, Abuja, Nigeria

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Both the single-step deposition as well as the two-step was obtained from Dyesol. The dehydrated lead acetate
sequential spin coating are solution-processed that require [Pb(Ac)2] was obtained by the dehydration of ­PbAc2•3H2O
thermal annealing, and are suitable in mass and cost-effec- under a flowing nitrogen gas at 80 °C. The precursor was
tive production. Hence, the composition of the precursor prepared by dissolving 3.0  mmol MAI and 1.0  mmol
solution, the rate of evaporation of the by-product from the Pb(Ac)2 in 1 mL dimethylformamide (DMF) solvent.
film and the annealing temperature have a direct influence on
the rate of crystallization, size of the crystals and film mor- Device fabrication
phologies [17]. At the early phases of spin coating, the sol-
vent vaporizes rapidly, and the crystallization rate of the per- The architecture of the solar cell devices was ITO/
ovskite is greatly lowered due to the presence of the surplus PEDOT:PSS/CH3NH3PbI3/PCBM/Ag. The patterned glass/
organic constituent in the film; however, the crystallization indium tin oxide (ITO) substrates were cleaned in a soap
procedure can further be improved by thermal anneal pro- solution, deionized water, acetone and isopropyl alcohol
cess of the film to evaporate the surplus organic by-product in an ultrasonic bath for 14 min. Finally, they were treated
[18]. During this process, the combinatory by-product of the by exposing to ultraviolet-ozone (UVO) for 14 min to get
anneal and evaporation results in pinhole formation within rid of any remaining impurity. The hole transport layer
the final crystalline layer. However, by manipulating suc- of PEDOT:PSS was filtered through a 0.45 μm filter and
cessfully the growth of the perovskite layer and the nuclea- the filtered solution was spin coated onto the patterned
tion an excellent perovskite film can be obtained by one-step ITO substrates at a spin-coating rate of 4000 rpm for 60 s
spin coating method; thus, controlling the crystallization before annealing at 135 °C for 15 min. The solutions of
process and the dynamics of film formation during coat- MAI:Pb(Ac)2 were then spin coated on the PEDOT:PSS
ing, before annealing and during annealing are important to layer at the rate of 4000 rpm for 60 s before they were ther-
the optimization of film morphology. Based on this consid- mally annealed on the hot plate at the temperatures of 80 °C,
eration different approaches have been developed from the 85 °C, 90 °C and 95 °C for 5 min, respectively. These pro-
areas of precursor selection [18–22], solvent engineering and cesses resulted in perovskite films.
solvent annealing [23, 24], fast deposition–crystallization After that, the electron collection layer of phenyl-C61-bu-
[25], thermal annealing [26], interface engineering [27] and tyric acid methyl ester (PCBM, Aldrich) was obtained by
processing additive [8, 28]. dissolving the solutes into a chlorobenzene solvent (20 mg/
Recently, lead acetate [Pb(Ac)2] has been used as the mL) and spin coating it on ­CH3NH3PbI3 layer at the rate
lead source in the preparation of perovskite films by one- of 1500 rpm for 30 s. Lastly, the silver (Ag) electrode was
step spin coating process [29–31]. One of the advantages deposited on the PCBM to complete the device fabrication
of Pb(Ac)2 is that it accelerates the crystal growth of per- process. The fabricated device is an inverted planar hetero-
ovskite due to the facile removal of N-methylammonium junction solar cell (see Fig. 1b). The dimension of the sub-
acetate ­(CH3NH3Ac) [32]. As a result, smooth films with strate is 2.5 cm × 2.5 cm and the active area is 0.2 cm2. These
fewer pinholes are achieved, which result in a better device sets of devices were vetted to determine the optimal thermal
performance. annealing temperature. The next set of devices was for deter-
Herein we report the preparation of a one-step, low-tem- mining the optimal pre-thermal annealing aging time.
perature solution process to produce smooth C ­ H3NH3PbI3 In this set of devices the same experimental procedure
layers free of pinholes, with dehydrated Pb(Ac)2 as the was followed as explained above, but after the deposition of
source material. Excellent perovskite films can be obtained the Pb(Ac)2:MAI solutions the films were allowed to age for
by pre-thermal anneal aging for 200 s before thermal anneal- 0 s, 200 s and 600 s before they were thermally annealed at
ing at 90 °C for 5 min, which can deliver high power conver- 90 °C for 5 min. After that, the PCBM solution was obtained
sion efficiency (PCE) of 13.02% with high repeatability of by dissolving its 20 mg/mL in a chlorobenzene. The PCBM
the device. Only a few works have been done using dehy- solution was then spin coated on the perovskite layer at the
drated lead acetate as the source material. This may have rate of 1500 rpm for 30 s to obtain the electron collection
been attributed to its low repeatability. layer. Finally, the silver (Ag) electrode was deposited on the
PCBM to complete the device fabrication process.

Experimental Device characterization

Materials The samples were characterized by scanning electron

microscopy (SEM) to observe the surface morphologies of
Lead acetate trihydrate (­PbAc 2•3H 2O) was purchased the samples [SEM-XL30 Environmental FEG (FEI)]. The
from Alfa Aesar, while methylammonium iodide (MAI) Cary 5000 UV/VIS spectrometer was used for measuring

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Materials for Renewable and Sustainable Energy (2019) 8:3 Page 3 of 10  3

Fig. 1  A schematic representation of the perovskite solar cell fabrication process, a thermal annealing immediately after spin coating, b the
architecture of the device, c pre-annealing aging after spin coating

the absorption spectra. The X-ray diffraction (XRD) pat- out of the precursor, removal of the unwanted salt from the
terns were observed by diffractometer (40 kV tension and film and evaporation of stoichiometric MAI from the perovs-
40 mA filament current) using Cu Kα radiation at a step- kite lattice [33]. These steps happened during spin coating,
size of 0.01°. The current density–voltage (J–V) values of aging and annealing process. During spin coating, solvents
the fabricated solar cells were observed on a Keithley 2400, are evaporated out of the solution; however, some of the
under simulated AM1.5G irradiation (100 mW/cm2) with a solvents will remain in the solution which requires anneal-
Xenon-lamp-based solar simulator (Spectra Physics, Oriel ing for the complete removal of the solvent (DMF). The
Instruments, USA). evaporation rate of the volatile by-products (­ CH3NH3Ac)
has a great impact on the rate of formation of perovskite film
[29]. Figure 2c and d presents the morphologies of samples
Results and discussion annealed at 90 °C and 95 °C. The good morphology of these
samples is as a result of the complete evaporation of the
The SEM images representing morphologies of the per- volatile by-products ­(CH3NH3Ac), and the 90 °C annealing
ovskite films on ITO/PEDOT:PSS substrates are shown in temperature is just sufficient to provide the latent heat of
Figs. 2 and 3. Figure 2a–d shows the morphologies of films vaporization needed for the complete removal of the by-
obtained with a thermal annealing at temperatures of 80, products ­(CH3NH3Ac).
85, 90 and 95 °C for 5 min, respectively. The entire samples Figure 3 shows SEM images of perovskite films aged at
show uniform film coverage irrespective of the annealing 0, 200, and 600 s before annealing at 90 °C for 5 min. The
temperature, however, the crystallinity improves with tem- images show densely packed grains over the entire area and
perature, and the uniform film coverage observed in all the no visible pores are observed in the perovskite films. From
samples is one of the advantages of lead acetate as a source the SEM images, the thin films annealed at 90 °C exhibit a
material for perovskite solar cells. Figure 2a–b shows dense better film coverage, improved grain sizes and crystallinity;
film coverage with poor crystal growth and small grain sizes. however, no noticeable difference in the morphologies of
The poor morphologies observed are attributed to the incom- the samples aged at 0–600 s before annealing at 90 °C for
plete evaporation of the by-products methyl ammonium ace- 5 min. In general, the films annealed at 90 °C have excellent
tate ­(CH3NH3Ac) from the films annealed at temperatures morphologies.
of 80 and 85 °C. As a result of the insufficient annealing Figure 4 represents the XRD pattern of the perovskite
temperature and annealing time [16, 17], the by-products films annealed at 80, 85, 90 and 95 °C, respectively. Films
present in the films create sites for pinholes and poor crys- annealed at 80, 85, and 90 °C show prominent diffraction
tal formation which are caused by the decomposition of peaks at 14.19 and 28.45, corresponding to (110) and (220)
­CH3NH3Ac in the film. Moore et al. reported that four stages lattice planes of the perovskite phase of C ­ H 3NH 3PbI 3,
are involved in the formation of perovskite films: vaporiza- respectively. The highest peak intensity of perovskite layer
tion of the solvent, spreading of the surplus irrelevant salt is achieved at 90 °C, the peaks (110) and (220) intensity

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Fig. 2  Surface morphologies of perovskite films annealed at the temperatures of a 80 °C; b 85 °C; c 90 °C; and d 95 °C, respectively, for 5 min

Fig. 3  SEM images of films aged at different time of a 0 s; b 200 s and c 600 s, before thermal annealing at 90 °C for 5 min

of Fig. 4 increase with increase in temperature up to the This is consistent with the results obtained from the SEM
optimal temperature at 90 °C, beyond this temperature images (see Fig. 5) which show that the optimal pre-anneal
the intensity of peaks (110) and (220) decreased, indicat- aging time is 200 s and also corresponded to the highest
ing that the crystallinity of the perovskite layer improves peak intensities of (110) and (220), respectively. The XRD
with temperature until the optimal temperature of 90 °C. results show that the aging process has an influence on the

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has an impact on the quality of perovskite film, which is

4000 80 o C
(110) (220) due to the controlled rate of the removal of ­CH3NH3Ac.
2000
0
The rate of removal of ­CH3NH3Ac has a great contribution
o in the perovskite film formation [29].
Intensity (a.u.)

4000 (110) (220) 85 C

2000
The Scherrer’s equation is adopted in calculating the crys-
0 tal size from the XRD patterns. The (110) peak from Fig. 4
4000 (110) o
90 C indicates that the full width at half maximum (FWHM)
(220)
2000 decreases with increase in the annealing temperature from
0 80 to 90 °C, which translate into an increase in crystallite
4000
(110)
o
95 C size with increase in the annealing temperature. The high-
2000 (220)
0
est grain size is obtained at 90 °C and decreases with an
10 20 30 40 50 increase in temperature above 90 °C; (see supporting doc-
2 theta (Deg.) ument; Table S2) this is due to the complete removal of
­CH3NH3Ac from the film and providing good crystallinity
Fig. 4  XRD patterns of the films annealed at 80 °C, 85 °C, 90 °C and at 90 °C. This also agrees with SEM images in Fig. 3. The
95 °C
samples aged at 200 s show a slight increase in the grain
sizes compared to those aged at 0 s and 600 s, respectively
0s
(Table S3).
4000
(110) (220)
Figure 6 represents UV–Vis spectra of the C ­ H3NH3PbI3
2000
films fabricated on glass substrates with annealing tempera-
0
tures of 80, 85, 90, and 95 °C. The high absorbance observed
Intenssity (a.u.)

(110) 200s
4000
(220)
for film annealed at 80 °C can be ascribed to the develop-
2000 ment of pinholes and to the poor crystal formation of the
0 perovskite film and this is also noticed in the SEM images.
4000 Figure 7a shows the absorbance spectra of films aged after
600s
2000 (110) (220)
spin coating before annealing at 90 °C for 5 min; however,
no noticeable difference in the optical absorbance of sam-
0
10 20 30 40 50 ples derived from different pre-annealing aging time. These
2 theta (Deg.) results show that pre-annealing aging has no effect on the
optical absorption.
Fig. 5  XRD patterns of the films aged at 0 s, 200 s, and 600 s before To further understand the effect of pre-annealing aging
annealing at 90 °C for 5 min
on the performance of perovskite films, TCPL spectra and
steady-state photoluminescence (PL) spectra characteriza-
peak intensity of the perovskite film. However, a further tion is done. The steady-state PL spectra of the perovskite
increase in the aging time decreases the (110) and (220) films deposited on glass show that the films aged at a differ-
peak intensities of the perovskite film. The pre-annealing ent time show the same peak position, as shown in Fig. 8a.
aging process allows for nucleation to take place at room No red-shift or blue-shift photoluminescence spectra are
temperature. During the later stage of the spin coating and observed; this implies that there is no change in the band
during the pre-annealing aging process the film changes gap and the grain size of the perovskite films aged at a dif-
color gradually from transparent to reddish-brown. This ferent time. Time-resolved photoluminescence has been used
shows that nucleation partly takes place during the later extensively in perovskite solar cell to investigate the charge
stages of the spin coating and during the pre-annealing carrier dynamics [3, 4]. Figure 8b shows the TCPL spectra
aging process. Therefore, from the changes observed in the of the samples aged at a different time. The observed PL
film, it is believed that perovskite nucleation partially takes decays are fitted with two exponential decay curves to yield
place during pre-annealing aging and leads to the reduc- the lifetime of excitons or carriers according to the one-
tion in the amount of ­CH3NH3Ac that will be evaporated dimensional diffusion model, as summarized in supporting
out of the film during the thermal annealing process. The information (Table S1). The fast decay component (τ1) and
gradual removal of a small quantity of ­CH3NH3Ac during the slow decay component (τ2) could be attributed to non-
annealing leads to an improvement in the grain growth radiative recombination and free carriers recombination,
of the film as it is observed in the XRD peak intensity respectively [3]. The PL lifetimes for perovskite film derived
of the perovskite. The effect of the pre-annealing aging from 200 s pre-annealing aging time are τ1 = 1.54 ns and
is clearly observed in the XRD pattern in Fig. 5. These τ2 = 37.66 ns; both values of the lifetime are slightly higher
results indicate that controlling the pre-annealing aging compared to the samples aged at 0 and 600 s.

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(a) 4 (b) 80

3 60

Transmittance (%)
Absorbance (a.u.)

80 °C
85 °C
2 40 80 °C
90 °C
95 °C 85 °C
90 °C
1 20 95 °C

0 0
400 500 600 700 800 400 500 600 700 800
Wavelenght (nm) Wavelength (nm)

Fig. 6  a Absorption and b transmittance spectra of perovskite films annealed at different temperatures

(a) (b) 80

0s
3
200s
60 600s
Transmittance (%)
Absorbance (a.u.)

2
40

1 0s
20
200s
600s

0 0
400 500 600 700 800 400 500 600 700 800
Wavelenght (nm) Wavelenght (nm)

Fig. 7  a Absorption and b transmittance spectra of perovskite films annealed at 90 °C and aged at different time

A planar heterojunction architecture was adopted as pre- Different thermal annealing temperatures and pre-
sented in Fig. 1b to study the impact of pre-annealing aging thermal annealing aging time were considered in fabricat-
on the photovoltaic performance of the perovskite solar cell ing the device with a structure of glass/ITO/PEDOT:PSS/
with dehydrated lead acetate Pb(Ac)2 as the source mate- CH 3 NH 3 PbI 3 /PCMB/Ag. The J–V curves of devices
rials. The perovskite layer (­ CH3NH3PbI3) is sandwiched annealed at 80 °C, 85 °C, 90 °C and 95 °C are shown in
between the hole transport layer PEDOT:PSS and the elec- Fig. 9. The device characteristics shown in Table 1 reveal
tron transport layer PCBM. When the light enters the mul- that devices annealed at 90 °C have the best performing
tilayered device from the glass/ITO side, the photoactive PCE of 10.8% and sample annealed at 80 °C has the lowest
layer absorbs the photons to produce excitons and mobile PCE of 5.3%. The low PCE in the devices annealed at 80
charge carriers. In a simple thin-film planar heterojunction and 85 °C is as a result of the incomplete removal of the
structure-based PV devices, it is possible for materials with ­CH3NH3Ac from the film. This results in the poor crystal
long diffusion length to have the charge carriers to migrate growth and defects in the films as it is observed in the SEM
through the entire photoactive layer. images (Fig. 2a, b), these defects serve as recombination

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Materials for Renewable and Sustainable Energy (2019) 8:3 Page 7 of 10  3

Fig. 8  a Steady-state PL spectra and b time-resolved PL curves of perovskite films prepared from solution derived from different pre-annealing
aging time. All the samples are annealed at 90 °C for 5 min

o
0 80 C
Current density (mA/cm )
2

o
85 C
o
90 C
-5 o
95 C

-10

-15

-20

-0.2 0.0 0.2 0.4 0.6 0.8

Voltage (V)
Fig. 10  J–V curves of devices obtained with different aging time

Fig. 9  J–V curves derived from different annealing temperatures

Table 2  Photovoltaic properties of devices obtained from pre-anneal-

Table 1  Photovoltaic properties of devices obtained from annealing ing aging of 0  s, 200  s and 600  s, respectively, before annealing at
temperatures of 80 °C, 85 °C, 90 °C and 95 °C, respectively 90 °C for 5 min

Temperature Voc (V) Jsc (mA/cm2) FF (%) PCE (%) Aging time (s) Voc (V) Jsc (mA/cm2) FF (%) PCE (%)
(°C)
0 0.94 20.71 63.00 10.80
80 0.71 20.09 33.50 4.80 200 0.98 22.50 60.00 13.02
85 0.88 18.73 42.40 7.00 600 0.97 20.52 65.00 12.84
90 0.90 19.50 61.10 10.80
95 0.87 20.30 48.10 8.60

imbalance of charge carrier mobilities in planar heterojunc-

tion solar cells [34], electrons and holes cannot be extracted
sites for the charge carriers and directly lead to low PCE. sufficiently fast due to poor crystal growth of the device
The S-shape characteristics of the J–V curve observed for annealed at 80 °C. The concentration of the charge carriers
the device annealed at 80 °C could be as a result of the at the interface of the electron transport layer and the hole

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Fig. 11  PCE histogram of 50 devices derived from a annealing immediately after spin coating and b aging after spin coating before annealing

transport layer is increased which leads to a high probabil- Conclusions

ity of recombination and hence a low fill factor (FF). The
charge transport properties of the active layer are responsible The impact of pre-annealing aging on the photovoltaic prop-
for the S-shape J–V curve. In contrast, the improved PCE erties of perovskite solar cells fabricated from dehydrated
in the devices annealed at 90 °C and 95 °C is as a result lead acetate (Pb(Ac)2)-based precursor using a single-step
of complete evaporation of the C ­ H3NH3Ac from the film. deposition method was investigated. The as-prepared film
Figure 10 shows the J–V curves of samples aged at 0, 200, exhibits uniform coverage with lesser pinholes with excel-
and 600 s before annealing at 90 °C for 5 min, results from lent morphology and crystallinity. The PCE of solar cell
Fig. 10 and Table 2 show that the best PCE of 13.02% is devices derived from aging after spin coating before thermal
obtained for a 200 s pre-annealing aging time. The increase annealing averages 13.02% with high repeatability, which
in the PCE is due to the partial removal of C ­ H3NH3Ac dur- is far higher than devices obtained from thermal annealing
ing aging and this results in the gradual removal of small immediately after the spin with a PCE of 10.8% and lower
amount of ­CH3NH3Ac during thermal annealing. In the case repeatability. The reason for the improved performance and
of the unaged devices that are annealed immediately after higher reproducibility is a result of the gradual removal of
spin coating, there is an abrupt removal of a large amount of small amounts of ­CH3NH3Ac during thermal anneal for
­CH3NH3Ac creating defects in the devices and these defects the aged samples as compared to the abrupt removal of
lead to the recombination of charge carriers before getting ­CH3NH3Ac for the unaged samples. Our findings suggest
to their respective transport layers. that pre-annealing aging has a great impact on the perfor-
Figure 11a, b shows the PCE histogram of 50 devices mance of solar cell devices derived from dehydrated lead
derived from annealing immediately after spin coating and acetate used as the source materials.
aging after spin coating before annealing, respectively. The
results from Fig. 11b show that devices derived from pre- Acknowledgements  This research was funded by Pan African Materi-
annealing aging show higher repeatability. The justification als Institute (PAMI) through funding from the World Bank to whom
the authors are grateful.
for the high reproducibility in these devices is due to the
fact that during aging nucleation partly takes place and also Open Access  This article is distributed under the terms of the Crea-
­ H3NH3Ac takes place. Thus,
the partial evaporation of the C tive Commons Attribution 4.0 International License (http://creat​iveco​
during the thermal anneal, small quantities of C ­ H3NH3Ac mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribu-
are gradually removed from the film and lead to an improved tion, and reproduction in any medium, provided you give appropriate
credit to the original author(s) and the source, provide a link to the
grain growth, high PCE, and high repeatability. The low Creative Commons license, and indicate if changes were made.
reproducibility in the unaged devices is due to the abrupt
removal of a large amount of C ­ H3NH3Ac during the ther-
mal anneal. This creates defects in the films which provide
recombination sites for the mobile charge carriers and in
some cases complete device failure.

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Materials for Renewable and Sustainable Energy (2019) 8:3 Page 9 of 10  3

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