Solar Energy 174 (2018) 933–939

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Photoelectric performance and stability comparison of MAPbI3 and FAPbI3 T

perovskite solar cells
Qingbo Weia, Wei Zib, Zhou Yangb, Dong Yangb,
⁎

a
Key Laboratory of Chemical Reaction Engineering of Shaanxi Province, College of Chemistry & Chemical Engineering, Yan'an University, Yan'an 716000, PR China
b
Key Laboratory of Applied Surface and Colloid Chemistry of the Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Chemistry
and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, PR China

ARTICLE INFO ABSTRACT

Keywords: Absorption layer plays a very important role in the high efficiency and stability perovskite solar cells, there have
Perovskite been many reports that based on CH3NH3PbI3 (MAPbI3) and NH2CH]NH2PbI3 (FAPbI3) perovskite solar cells,
Solar cells but the system compares the performance differences between MAPbI3-based and FAPbI3-based perovskite solar
Thin films cells. The MAPbI3 and FAPbI3 perovskite solar cells are differences in topography, optical performance, the
Stability
performance of solar cells, and device stability. It is particularly noteworthy that we calculated the defect state
density and carrier mobility of the device under dark current. Through the construction of the solar cells, it has
been found that the planar FAPbI3 perovskite solar cells have better photoelectric conversion efficiency. The
FAPbI3 solar cells show superior performance compared to the MAPbI3-based devices, the power conversion
efficiency of 16.38% and 18.61% was obtained with high short circuit current density of 21.11 and 23.18 mA/
cm2.

1. Introduction hybrid perovskite materials that possess high absorption coefficients,

Hybrid organic-inorganic perovskite solar cells have experienced an
explosive development, with a power conversion efficiency quickly
rising from the 3% to 22.7%, due to their excellent advantages in-
cluding wide optical absorption, high carrier mobility and long life-time
(Jeon et al., 2015; Kojima et al., 2009; Kim et al., 2012; Xing et al.,
2013; Yang et al., 2015a, 2015b; Zhou et al., 2014). In the characteristic
ABX3 perovskite structures, A and B represent various metal compound
cations and X is the anion, such as Br, Cl, I or the mixed ratio of ha-
logens. Adjusting the composition can significantly decide the optoe-
lectronic properties of perovskites (Hao et al., 2014; Koh et al., 2014; Lv
et al., 2014; Yin et al., 2015).
Methylammonium (MA) cation in the A site is so far the most ex-
plored perovskite composition in the past few years. However, the band
gaps of the MA-based perovskite absorbers are generally larger than
1.55 eV, causing the narrow Optical absorption range, and low photo-
electric conversion efficiency. In this regard, FAPbI3 has been devel-
oped as a more effective, absorber, with a narrower band gap of 1.47 eV
compared to MAPbI3. More importantly, materials and processes have
been developed to solve the stability problem. Therefore, FA is used to
replace MA to reduce the bandgap toward a more ideal range (Lee et al.,
2014a; Zhao et al., 2015). Also researchers used the organic/inorganic
appropriate bandgap, and long-lived charge carriers with high mobility
(Dong et al., 2015; Lee et al., 2014b, 2015; Koh et al., 2014; Lin et al.,
2015; Ryu et al., 2014; Stranks et al., 2013; Xiao et al., 2015) to get
good achievement.
In this study, we have constructed high efficiency and stability
planar-structured MAPbI3 and FAPbI3 perovskite solar cells were pre-
pared via a single-step deposition process. With a single-step deposition
process, the MAPbI3 and FAPbI3 perovskite layer showed high crystal-
linity, large grain size, full surface coverage and high efficiency and
stability. We also calculated the defect state density and carrier mobi-
lity of the device under dark current. We obtained the FAPbI3 and
MAPbI3 perovskite solar cells of power conversion efficiency are
16.38% and 18.61% respectively.
2. Results and discussion
XRD was conducted to characterize the crystal structure of each
perovskite sample prepared on the TiO2-coated FTO substrates. Fig. 1a
showed diffraction peaks of the MAPbI3 perovskite film located at
14.08°, 28.40°, and 31.86°, corresponding to the (1 1 0), (2 2 0), and
(3 1 0) lattice planes, respectively (Quarti et al., 2014). And the dif-
fraction peaks located at 14.2°, 19.9°, 24.3°, 28.4°, 31.7°, 34.7°, 40.5°,

⁎
Corresponding author.
E-mail address: dongyang@snnu.edu.cn (D. Yang).

https://doi.org/10.1016/j.solener.2018.09.057
Received 5 July 2018; Received in revised form 18 September 2018; Accepted 21 September 2018
0038-092X/ © 2018 Elsevier Ltd. All rights reserved.
Q. Wei et al. Solar Energy 174 (2018) 933–939

Fig. 1. Typical XRD patterns (a) and UV–Vis-NIR spectra (b) of the MAPbI3 and FAPbI3 perovskite films.

Fig. 2. AFM and SEM images of the MAPbI3 (A, C and E) and FAPbI3 (B, D and F) perovskite films.

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Q. Wei et al.
Fig. 3. XPS spectra of MAPbI3 and FAPbI3 perovskite film coated on FTO
substances.
and 42.7° is attributed correspondingly to the (1 1 1), (1 2 0), (0 2 1),
(2 2 2), (2 3 1), (0 3 0), (2 4 0) and (3 3 3) lattice planes for FAPbI3
perovskite film, respectively, in good agreement with the previously
report (Eperon et al., 2015; Stoumpos et al., 2013). The diffraction
peaks shift toward lower degrees compared with the MAPbI3 due to the
replacement of the smaller CH3NH3+(MA) cation with the larger
NH2CH]NH2+ (FA) (Yuan et al., 2015). As can be seen from Fig. 1,
FAPbI3 perovskite films show a partial lead iodide peak, but not in the
MAPbI3 perovskite film. Excess lead iodide is beneficial to passivate the
grain boundaries and improve the film quality. Fig. 1b shows the
UV–vis absorption spectra of MAPbI3 and FAPbI3 perovskite films. In
the range of 550–810 nm, the UV–vis absorption of FAPbI3 perovskite
film is stronger than that of MAPbI3. The absorption extends over the
complete visible spectrum up to 760 nm and 810 nm, in agreement with
earlier publications. The wider of the absorption range, the greater the
intensity, and the higher the photoelectric conversion efficiency.
Therefore, the short-circuit current of the FAPbI3 perovskite solar cells
is higher than that of MAPbI3.
The morphology of the perovskite thin films is further evaluated by
atomic force microscopy (AFM) and field emission scanning electron
microscope (FE-SEM). As shown in Fig. 2, the as-synthesized perovskite
films on TiO2-coated FTO substrate have large grain size up to micro-
meter scale with good surface coverage. The root-mean-square (RMS)
surface roughness of MAPbI3 and FAPbI3 perovskite films were esti-
mated from AFM images (Fig. 2A and B) to be 10.8 and 43 nm, which is
as small as the roughness of the film fabricated via other evaporation
methods regardless of its large grain size. The large grain size may serve
to increase the carrier mobility within perovskite film and reduce re-
combination. With the combination of encouraging characteristics in-
cluding full surface coverage, large grain size, long-range continuous
and homogeneous thin-film morphology and high level of crystal-
lization phase purity, one can anticipate promising photovoltaic per-
formance by incorporating the perovskite thin films in the devices
(Chen et al., 2014; Yang et al., 2015a, 2015b). SEM images in Fig. 2C
and D show the MAPbI3 and FAPbI3 films were smooth and homo-
genous without pin-holes and voids. The large grain size can be related
to volume expansion during the reaction and intercalation of PbI2 with
MAI (or FAI), as well as to the rearrangement of the perovskite structure
driven by the reduction of grain boundaries due to the minimized grain
boundary energy. It can be clearly seen from the figure that the grain
size of the FAPbI3 film is significantly larger than that of the MAPbI3
perovskite film. Fig. 2E and F present cross-sectional SEM images of the
MAPbI3 and FAPbI3 solar cells, showing a sandwich structure, which is
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Solar Energy 174 (2018) 933–939
a typical layer structure for plane perovskite solar cells. The thickness of
perovskite layer is about 500 nm, which is in the optimized range for
efficient light harvesting and electron transfer, from Fig. 2E, we can
clearly observe the MAPbI3 perovskite crystallites, while FAPbI3 is a
large grain with no grain boundaries. From the figure we can clearly see
that the interface layers are tightly combined. Therefore, it is effective
to ensure the transmission of electrons and holes. The compact TiO2
worked as a electron transfer layer and the thickness is about 50 nm.
The spiro-MeOTAD acts as a hole-conducting layer and the thickness is
about 200 nm, so that the photogenerated electrons and holes from
perovskite can be efficiently separated.
The results of XPS measurement were summarized in Fig. 3. The C
1s peaks located at 280.58 eV, 136.26 eV and 870.33 eV are attributed
to C 1s, Pb4f and I3d, respectively, in good coincidence with the values
in the reference (Ke et al., 2016). The two perovskite films contain the
same elements, so the XPS measurement results are basically the same.
As shown in Fig. 4, thermal gravimetric analysis (TGA) and differential
scanning calorimetry (DSC) analysis are used to determine the mass loss
behavior of the individual organic and inorganic components that make
up the building blocks of MAPbI3 and FAPbI3 perovskite as a function of
temperature. The decomposition temperature are 320 and 337 °C for
MAPbI3 and FAPbI3, respectively, indicating that MAPbI3 and FAPbI3
films are still intact after annealing at 100 °C (150 °C) for 15 min, which
is utilized in the devices fabrication process. Intriguingly, FAPbI3
sample shows high sublimation temperature at the first step, indicating
a better thermal stability of FAPbI3 perovskite film.
The steady-state photoluminescence (PL) measurement is applied to
investigate the charge carrier recombination behavior in bulk per-
ovskite and at the TiO2/perovskite interface. A considerable decrease in
PL intensity was observed for the perovskite film in contact with both
doped TiO2 and FTO. The enhanced quenching indicates effective
charge extraction, which is in good agreement with the remarkable
performance displayed by both HTMs. Fig. 5(a) shows that MAPbI3 and
FAPbI3 perovskite films emit at 766 nm and 810 nm, respectively. The
band-gaps for MAPbI3 and FAPbI3 are estimated to be 1.6 eV (776 nm)
and 1.5 eV (810 nm), respectively, which is in a good agreement with
previous reports (Liu et al., 2014; Shi et al., 2014; Sun et al., 2014; Xie
et al., 2015). As both MAPbI3 and FAPbI3 have broad absorption cov-
ering the entire visible range (400–810 nm), they are suitable candi-
dates for photovoltaic applications. Also, it is possible to obtain a high
photo-to-electric conversion efficiency due to relatively flat absorption
curve in the visible spectrum. FAPbI3 exhibited the higher PL signal and
thus a higher recombination rate of carriers in comparison to MAPb3
samples. Fig. 5(b) displays the TRPL spectra of the FTO/TiO2/MAPbI3
and FTO/TiO2/FAPbI3 films. The key TRPL parameters are listed in
Table 1. The decrease exciton lifetime indicates the reduced re-
combination in the FTO/TiO2/FAPbI3 film. The exciton lifetime in-
dicative of the recombination behavior of the FTO/TiO2/MAPbI3 and
FTO/TiO2/FAPbI3 films affect the devices performance, the exciton
lifetime (13.17 ns) of the FTO/TiO2/FAPbI3 film is lower than that of
the FTO/TiO2/MAPbI3 film (29.04 ns). The FAPbI3 solar cells show a
better performance than MAPbI3. We also attribute this phenomenon to
inferior crystallization. Compared to the MAPbI3 film, the FAPbI3 film
has larger grains, and reduced the charge recombination, resulting in
increased Jsc and Voc values for the FAPbI3 solar cells. Fig. 5(c) presents
Nyquist plots of MAPbI3 and FAPbI3 devices at a voltage bias of 0.9 V
under dark. For the devices of MAPbI3 and FAPbI3, the data in the
Nyquist plot contain one distinct semi-circle, at low frequencies region,
which should be attributed to the charge transfer resistance between
TiO2 and perovskite absorber. In the MAPbI3 and FAPbI3 perovskite
absorber solar cells, the dominant electron loss pathway is the re-
combination of electrons from the TiO2 to perovskite absorber. As
shown in low frequency response, the recombination resistance of
FAPbI3 device is larger than MAPbI3 device, indicating a smaller re-
combination rate of FAPbI3 device. The results reveal that higher per-
formance of the FAPbI3 device.
Q. Wei et al. Solar Energy 174 (2018) 933–939

Fig. 4. Thermal analysis of the MAPbI3 (a) and FAPbI3 (b) perovskite power.

800
FAPbI3~ 810nm (a) (b)
MAPbI3~766 nm
MAPbI3
600 FAPbI3
PL Intensity (a.u.)

Intensity (a.u.)

400

200

700 750 800 850 900 0 20 40 60 80 100

Wavelength (nm) Time (ns)

1250
(c)

1000
FAPbI3

750
Z''(Ohm)

500
MAPbI3
250

0
0.0 500.0 1.0k 1.5k 2.0k 2.5k
Z'(Ohm)
Fig. 5. (a) Photoluminescence spectra of the MAPbI3 and FAPbI3 perovskite films; (b) TRPL spectra of the FTO/TiO2/MAPbI3 and FTO/TiO2/FAPbI3 films; (c) Nyquist
plots of MAPbI3 and FAPbI3 solar cells under dark at the same applied voltage, 0.90 V.

The photocurrent density-voltage (J-V) characteristics of the
MAPbI3 and FAPbI3 solar cells are shown in Fig. 6a. The MAPbI3 cell
achieved about 16.38% power conversion efficient (PCE), with a short-
current photocurrent (Jsc) of 21.11 mA/cm2, an open circuit voltage
(Voc) of 1.08 V and a fill factor (FF) off 0.72. In contrast, the cell of
FAPbI3 exhibited a PCE of 18.61% (Jsc = 23.18 mA/cm2, Voc = 1.1 V,
and FF = 0.73). It can be seen from Fig. 6a and Table 2 that there is a
large difference between the forward and reverse scans of the MAPbI3
battery, and the FAPbI3 battery has a small difference, so there is a
small hysteresis effect. These good photovoltaic parameters are attrib-
uted to the high crystallinity of the FAPbI3 phase, as well as the smooth
film surface without the presence of pinholes. The incident photon-to-
current conversion efficiency (IPCE) spectra in Fig. 6b show an oneset
of around 800 nm, and the Jsc obtained by integration of the IPCE
spectra agrees well with the Jsc obtained from the J-V measurement,
which attests to the consistency of our cell measurement. Fig. 6c shows

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Q. Wei et al. Solar Energy 174 (2018) 933–939

Table 1 Table 2
Fitting decay time of the FTO/TiO2/MAPbI3 and FTO/TiO2/FAPbI3 films. The parameters of the MAPbI3 and FAPbI3 divices.
Sample τave (ns) τ1 (ns) Amplitude of τ1 τ2 (ns) Amplitude of τ2 Sample Voc (V) Jsc (mA cm2) FF PCE%
(%) (%)
MAPbI3-RS 1.08 21.11 0.72 16.38
FTO/TiO2/MAPbI3 29.04 5.239 67.56 36.21 32.44 MAPbI3-FS 0.98 20.84 0.61 12.43
FTO/TiO2/FAPbI3 13.74 2.615 71.82 17.88 28.18 Average 1.03 20.98 0.67 14.39
FAPbI3-RS 1.1 23.18 0.73 18.61
FAPbI3-FS 1.08 22.73 0.71 17.44
Average 1.09 22.96 0.72 18.03
PCEs distribution of MAPbI3 and FAPbI3 solar cells of 30 individual
devices. As for the devices based on MAPbI3, PCE values were in the
range of 13.5–17% with a champion value of 16.38%, and the cells of The device dark current (JD) was measured to calculate the trap
FAPbI3 exhibited PCE from 15 to 19% with a champion value of density and carrier mobilities. The MAPbI3 and FAPbI3 films were
18.61%. Therefore, both perovskite solar cells have good repeatability, sandwiched by two Au electrodes deposited by thermal evaporation to
and the FAPbI3 solar cell efficiency is significantly higher than MAPbI3. form hole-only devices. As shown in Fig. 8a, the linear JD-V relation
The stability of the MAPbI3 and FAPbI3 solar cells were investigated indicates anohmic response at the low bias. A trap filling process was
in Fig. 7a. The obvious increase in the PCE in the first week can be identified by the marked increase of the current injection at a bias range
attributed to the slow oxidation of the spiro-MeOTAD, and after con- of 2.1–10.7 V. The voltage at which all the traps are filled (trap-filled
tinuously stored after more than one month, the PCE showed no ob- limit voltage VTFL) was determined by the trap density (Bube et al.,
vious decrease. The excellent stability is associated with the better 1962; Liu et al., 2015):
crystallinity and the compact and stable structure. Fig. 7b shows the entL2
photovoltaic performance during the long term aging test of the two VTFL =
2 0
devices. After 40 days of aging, the initial efficiency of 13.93% of the
MAPbI3 based cell decreased to 12.23%, giving a 12.20% reduction. On where L is the thickness of the MAPbI3 and FAPbI3 films (500 nm), e
the other hand, the initial efficiency of 14.33% of the FAPbI3 based cell (=32 and 62.23) are relative dielectric constant of MAPbI3 and FAPbI3,
also decreased to 13.24%, giving a 7.6% reduction. The higher stability and ε0 is the vacuum permittivity. The trap density nt in MAPbI3 and
of the FAPbI3 based cells is attributed to an interfacial tight packing due FAPbI3 films were calculated to be 6.5 × 1015 cm−3 and
to a planar and sterically bulky configuration. 2.7 × 1016 cm−3. For comparison, the hole-only devices with MAPbI3
and FAPbI3 films were also fabricated with PEDOT:PSS and Au as the

Fig. 6. (A) IPCE spectra of MAPbI3 and FAPbI3 devices, where the integrated Jsc were calculated to be 21.32 mA cm−2 and 22.98 mA cm−2; (B) J-V characteristics of
MAPbI3 and FAPbI3 device respect to reverse and forward scan direction; (C) The PCE distribution histogram of the MAPbI3 and FAPbI3 planar-type cells.

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Q. Wei et al.
Fig. 7. Normalized PCE as a function of aging time for MAPbI3 and FAPbI3 solar cells.
Fig. 8. The MAPbI3 and FAPbI3 films of trap density and carrier mobilities.
hole injection electrodes (Fig. 8b). The calculated hole trap density in
the MAPbI3 and FAPbI3 films were 5.26 × 1015 cm−3 and
1.01 × 1016 cm−3, which is almost five orders of magnitude greater
than in the MAPbI3 and FAPbI3 films.
3. Conclusion
In summary, we have compared a facile one-step solution method
for fabrication of MAPbI3 and FAPbI3 perovskite solar cells. These
fabricated perovskite solar cells exhibited high crystallinity, large grain
size, full surface coverage, higher stability, the trap density and carrier
mobilities. A power conversion efficiency of 16.38% and 18.61% was
obtained with high short circuit current density of 21.11 and
23.18 mA cm2. FA-based devices show higher stability than MA-based
cells. By investigating the performance differences of MAPbI3 and
FAPbI3 perovskite cells, it is beneficial to optimize the cell structure and
build a highly efficient and stable perovskite solar cell. These reports
illustrate the potential and importance of studying FA-based solar cells
for future perovskite solar cell applications.
Acknowledgments
The authors acknowledge all the support from the National Natural
Science Foundation of China (61604090 and 61674098), the Key
Laboratory of Education department of Shaanxi Province (No. 15JS120)
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Solar Energy 174 (2018) 933–939
and Doctoral research initial funding from Yan’an University
(YDBK2017-14 and YDQ2018-15).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.solener.2018.09.057.
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