Applied Surface Science 403 (2017) 572–577

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Controlled growth of CH3 NH3 PbI3 films towards efficient perovskite

solar cells by varied-stoichiometric intermediate adduct
Yongguang Tu, Jihuai Wu ∗ , Xin He, Panfeng Guo, Hui Luo, Quanzhen Liu, Jianming Lin,
Miaoliang Huang, Yunfang Huang, Leqing Fan, Zhang Lan
Engineering Research Center of Environment-Friendly Functional Materials for Ministry of Education, Key Laboratory of Functional Materials for Fujian
Higher Education, College of Material Science and Engineering, Huaqiao University, Xiamen 361021, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: Lewis acid-base adduct approach with anti-solvent (diethyl ether) has been one of the efficient strate-
Received 5 November 2016 gies to prepare high-quality perovskite films for top-performing perovskite solar cells. Conventionally,
Received in revised form the molar ratio of CH3 NH3 I:PbI2 :DMSO in the precursor solution is 1:1:1, however, DMSO will be volatile
26 December 2016
alongside the extraction of DMF due to its miscibility with DMF solvent during the process of anti-solvent
Accepted 23 January 2017
washing, which introduces a non-stoichiometric intermediate adduct CH3 NH3 I·PbI2 ·xDMSO (x < 1). In
Available online 24 January 2017
this work, we increased the DMSO content in the Lewis acid-base adduct approach to enhance the con-
version efficiency of perovskite solar cells. More complete intermediate adduct CH3 NH3 I·PbI2 ·DMSO
Keywords:
DMSO
and wider window period of washing process ensure high-quality perovskite films and high repro-
Intermediate ducibility with raised content of DMSO. Furthermore, the devices prepared by the precursor solution
Crystallization of CH3 NH3 I:PbI2 :xDMSO (x = 2.0) exhibit high reproducibility and the best efficiency of perovskite solar
Perovskite solar cells cells is 17.84% under one-sun illumination.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction crucial for fabricating high-performance perovskite solar cells. Per-

Perovskite solar cells have aroused burgeoning interests for
making transformative surge [1–7] due to its many merits
such as broad and strong light absorption [8], longer car-
rier lifetimes [9], long charge carrier diffusion length [10], and
low exciton binding energy [11]. The most-studied perovskite
light absorbers are CH3 NH3 PbI3 [12], CH3 NH3 PbI3-x Clx [13] and
(NHCH2 PbI3 )0.85 (CH3 NH3 PbBr3 )0.15 [14]. Perovskite solar cells are
generally composed of transparent conducting oxide substrate
(TCO), a n-type compact blocking layer, perovskite layer with or
without scaffold layer (e.g TiO2 , ZnO or Al2 O3 ), a p-type hole-
transporting material (HTM) layer and metal back electrode [15].
The power conversion efficiency (PCE) have reached a high effi-
ciency of 20.8% [16], leapfrogging every other solution-processed
solar cell technology. More recently, an improved PCE of 22.1% was
certified by NREL (http://www.nrel.gov/ncpv/images/efficiency
chart.jpg).
The optoelectronic properties of perovskite films are closely
related to the film-quality [17,18], so perovskite deposition is
∗ Corresponding author.
E-mail address: jhwu@hqu.edu.cn (J. Wu).
ovskite film can be accomplished mainly using either one-step
coating [19–21] or sequential two-step coating [22–25]. Top-
performing perovskite solar cells usually are fabricated by a Lewis
acid-base adduct approach [26,27] with anti-solvent such as diethyl
ether, chlorobenzene or toluene to extract the solvents in the wet
perovskite film. Typically, in the Lewis acid-base adduct approach
to fabricate perovskite film, PbI2 and CH3 NH3 I is firstly dissolved by
mixture polar aprotic solvents, such as ␥-butylolacone (GBL), N,N-
dimethyl sulfoxide (DMSO), Thiourea, N,N-dimethylformamide
(DMF). As is known, iodide (I− ) in CH3 NH3 I is a strong donor
and could have a strong interaction with PbI2 , also DMSO is
deemed to be a Lewis base with O-donor, so intermediate adduct
of CH3 NH3 I·PbI2 ·DMSO is formed in the perovskite precursor
solution [21]. Then while the perovskite solution is spin-coated
on the mesoporous TiO2 layer, the anti-solvent (diethyl ether)
drips onto the rotating substrate, which leads to a transparent
CH3 NH3 I·PbI2 ·DMSO adduct film. Trace its root, diethyl ether is
miscible with DMF, but is immiscible with DMSO, so the sol-
vent DMF can be extracted quickly by diethyl ether, leading to
a uniform and homogeneous intermediate adduct film. However,
to obtain a high-quality perovskite film, the dropping rate and
time of diethyl ether is extremely crucial. Usually, the molar
ratio of CH3 NH3 I:PbI2 :DMSO in the precursor solution is 1:1:1,

http://dx.doi.org/10.1016/j.apsusc.2017.01.240
0169-4332/© 2017 Elsevier B.V. All rights reserved.
 Y. Tu et al. / Applied Surface Science 403 (2017) 572–577
Fig. 1. Schematics of the process of fabricating perovskite films by ameliorated Lewis acid-base adduct approach.
Fig. 2. Optical microscope of perovskite films after heat treatment in group of x = 1.0 at different dropwise time. Magnification of the microscope is 100.
DMSO will be volatile alongside the extraction of DMF due to
its miscibility with DMF during the washing process of anti-
solvent, which introduces a nonstoichiometric intermediate adduct
CH3 NH3 I·PbI2 ·xDMSO (x < 1). Intermediate adduct film will turn to
light brown owing to rapid crystallization of not quantitative per-
ovskite. Also, the window period of washing process of diethyl ether
is very narrow, which makes difficult to manipulate and reduces
reproducibility.
Herein, based on the Lewis acid-base adduct approach to fab-
ricate perovskite film, we improved the DMSO content in the
precursor solution to regulate the crystallization of perovskite
film by varied-stoichiometric intermediate adduct. The effects of
DMSO content on the perovskite film morphology, crystalliza-
tion, and device characteristics are discussed. Firstly, the degree
of red brown is obviously reduced, intimating more interme-
diate CH3 NH3 I·PbI2 ·DMSO adduct. Secondly, the time of film
changes turbid delays, the window period of the washing process
is broaden. Thirdly, the morphology and crystallization of per-
ovskite films can be fine-adjusted by tuning the content of DMSO.
Furthermore, the devices prepared by the precursor solution of
PbI2 :CH3 NH3 I:xDMSO (x = 2.0) exhibit high reproducibility and the
best efficiency of perovskite solar cells is 17.84% under one-sun
illumination.
2. Results and discussion
Fig. 1 shows the schematics of the process of fabricating per-
ovskite films by ameliorated Lewis acid-base adduct approach.
Perovskite films were fabricated by controlling different kinds
of precursor solutions with varying DMSO content. In first-step
program, removing excess precursor solution is a major process
[19], so introduction of diethyl ether should require an appropri-
ate point in time. In second-step program, most DMF could be
extracted by rapid evaporation of ether, and then the intermedi-
ate CH3 NH3 I·PbI2 ·DMSO will be crystalized by the supersaturation
from which a smooth and uniform film is formed [28].
To determine the precise time of introduction of the
diethyl ether, we studied three dropwise times in group of
x = 1.0:4000 rpm, 5th s; 4000 rpm, 7th s, 4000 rpm, 9th s, respec-
573
tively. Fig. 2 shows the optical microscope of perovskite films at
different dropwise time. For the sample of 5th s, there is a big crack
in the film, indicating that a large amount of solvent is remained in
the wet film and diethyl ether lashes the wet film. And the intro-
duction of diethyl ether is premature. For the sample of 9th s, there
are so many aggregates in the film, indicating that the intermediate
has been crystalized by the supersaturation and the introduction of
diethyl ether is too late. In this case, the window period would be
very narrow.
Then the time of films in six groups changed turbid were cen-
sus, 4000 rpm, 7th s for x = 0.5; 4000 rpm, 9th s for x = 1.0; 4000 rpm,
11th s for x = 1.5; 4000 rpm, 12th s for x = 2.0; 4000 rpm, 20th s for
x = 4.0; 4000 rpm, 28th s for x = 6.0, respectively. So the window
period becomes wide for the washing process as the content of
DMSO increased.
We recorded the color change of the films versus different
DMSO content to further scrutinize the crystal growth behav-
ior. Fig. 3 shows visual images of the perovskite film at different
time at room temperature. As shown in Fig. 3(a), the films show
different degree of hyperchromicity at the end of spin-coating.
As is known to all, the color of CH3 NH3 PbI3 is dark red, while
the color of CH3 NH3 I·PbI2 ·DMSO adduct is light white [21]. For
sample of x = 0.5, dark red-brown is the characteristic color, sug-
gesting the formation of perovskite. The degree of hyperchromicity
gradually decreased from group of x = 0.5 to group of x = 6.0. For
sample of x = 1.5, a brown transparent film was obtained. When
x > = 2.0, the film showed colorless transparent. So there are varied-
stoichiometric intermediate adducts in the incipient films. So a
conclusion can be drawn, with the increase of DMSO content
in precursor solution, the more complete CH3 NH3 I·PbI2 ·DMSO
intermediate adduct remained. Afterwards, when the time was
extended from 0 min to 60 min at room temperature, the color
of perovskite films of all groups was gradually deepened, indicat-
ing the slow crystallization introduced by the slow evaporation
of DMSO. And the effective regulation of crystal growth can be
achieved. For x = 6.0, the original colorless transparent also turned
brown.
Fig. 4 shows the waterfall XRD patterns of perovskite films
versus different DMSO content. The XRD patterns confirm the
574 Y. Tu et al. / Applied Surface Science 403 (2017) 572–577

Fig. 3. Photos of different group of perovskite films at different time at room temperature.

x=6.0
x=4.0
x=2.0
x=1.5
x=1.0
x=0.5

10 11 12 13 14 15 16
2 Theta (degree)
Fig. 4. The waterfall XRD patterns of perovskite films versus different DMSO con-
tent. Fig. 5. Magnified views of XRD patterns of perovskite films between 10◦ and 16◦ .

presence of the tetragonal perovskite phase of CH3 NH3 PbI3 in
all of the prepared films. The two main peaks located at 14.1◦
and 28.4◦ can be indexed to the (110) and (220) planes [29]. The
additional increase in the intensity indicates that the crystallinity
enhances as the DMSO content increases, which is ascribed to
strong Lewis basicity of DMSO. From x = 4.0 to x = 6.0, the intensity
shows dramatic downward, too much DMSO inhibits the crystal-
lization of the perovskite. So less DMSO is applied, the intermediate
CH3 NH3 I·PbI2 ·DMSO will be incomplete and perovskite crystals
fast, producing many traps and recombination centers. If too much
DMSO is applied, the excess DMSO remained in the wet film will
retard the crystallization. Fig. 5 shows the magnified views of XRD
patterns between 10◦ and 16◦ . And there is no excess PbI2 residue
in the film.
In order to investigate the surface morphologies of CH3 NH3 PbI3
films, we studied the top-view SEM images. As shown in Fig. 6, the
DMSO content has an obvious influence on the film’s grain size. In
group of x = 2.0 and group of x = 4.0, it presents an enlarged average
grain size, which would minimize the grain boundary energy and
be beneficial for the charge transmission.
Time resolved photoluminescence (TRPL) intensity decay mea-
surements of CH3 NH3 PbI3 perovskite films can be used to explore
the charge carrier extraction at the interface between TiO2 layer and
the perovskite layer [30], the samples were composed of FTO/CL-
TiO2 /mp-TiO2 /perovskite, and corresponding results are presented
 Y. Tu et al. / Applied Surface Science 403 (2017) 572–577 575

Fig. 6. Top-view SEM images of perovskite films versus different DMSO content.

104 25

20
Current Density (mA cm-2)
PL intensity (arb.units)

103
15
X=0.5
X=1.0
10
X=1.5
102 X=2.0
X=4.0
5
X=6.0

101 0
50 100 150 200 250 300 350 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Time (ns) Potential (V)

Fig. 7. Time-resolved photoluminescence intensity decay of CH3 NH3 PbI3 detected Fig. 8. J–V curves of the PSCs based on based on different DMSO content under AM
at peak emission wavelength of 760 nm. 1.5 G illumination. The devices were measured by reverse (2.0 v to −0.1 v) voltage
scanning at a scan step of about 21.2 mV (100 data points in total).
Table 1
Fitting parameters for the time-resolved PL measurements shown in Fig. 7. Table 2
Photovoltaic performances of the devices based on different DMSO content.
PbI2 :CH3 NH3 I:xDMSO A1 ␶1 /ns A2 ␶2 /ns Average␶/ns

x = 0.5 0.58 49.31 0.42 14.25 34.58 PbI2 :CH3 NH3 I:xDMSO Voc (V) Jsc (mA cm−2 ) FF (%) PCE (%)
x = 1.0 0.63 16.23 0.37 43.98 26.50 x = 0.5 1.012 20.89 67 14.16
x = 1.5 0.83 7.73 0.17 38.99 13.04 x = 1.0 1.035 22.13 69 15.80
x = 2.0 0.77 5.05 0.23 34.70 11.86 x = 1.5 1.052 22.35 69 16.22
x = 4.0 0.37 39.68 0.63 13.84 23.40 x = 2.0 1.076 23.03 72 17.84
x = 6.0 0.27 44.10 0.73 10.27 19.41 x = 4.0 1.049 22.80 71 16.98
x = 6.0 0.997 21.74 67 14.52

in Fig. 7. And the curves were fitted with a two exponential decay
function and the corresponding lifetimes were obtained, as listed
in Table 1. And the charge carrier lifetime (␶) are 34.58 ns, 26.50 ns,
13.04 ns, 11.86 ns, 23.40 ns, 19.41 ns, corresponding to the groups,
x = 0.5, 1.0, 1.5, 2.0, 4.0 and 6.0, respectively. The shorter ␶ value
means that the charge more fast transfer from the perovskite to
TiO2 layer [31–35], which may be attributed to the high crystallinity
and few grain boundaries.
J–V measurements of the perovskite solar cells based on dif-
ferent DMSO content are shown in Fig. 8 and the corresponding
photovoltaic parameters are listed in Table 2. For x = 0.5, a PCE
of 14.16% was achieved with short-circuit current density (Jsc) of
20.89 mA cm−2 , open-circuit photovoltage (Voc) of 1.012 V and fill
factor (FF) of 0.67. And the performance continuously improved
as the amount of DMSO increased. Compared to the devices from
group of x = 1.0 to group x = 4.0, the performance improvement
mainly lies in the increase of the Voc and the FF, depended largely
on the high-quality perovskite film. Best performance was achieved
in group of x = 2.0, yielding a Jsc of 23.03 mA cm−2 , Voc of 1.076 V,
and FF of 0.72, resulting in a PCE of 17.84%. Further increasing the
amount of DMSO in group of x = 6.0 did not improve device per-
576 Y. Tu et al. / Applied Surface Science 403 (2017) 572–577

24 24 100 25
22 22
Jsc=19.79mA·cm-2
Currenr Density (mA·cm-2)

20 20
80 20

Integrated Jsc (mA·cm-2)

18 18
16 PCE=17.25% 16
60 15

PCE (%)
14 14

IPCE (%)
12 12
10 10 40 10
8 8
6 6
20 5
4 4
Integrated Jsc=21.20mA·cm-2
2 2
0 0 0 0
0 100 200 300 400 300 400 500 600 700 800
Wavelength (nm)
Time (s)
Fig. 11. IPCE spectrum (black line) and integrated photocurrent density Jsc (red line)
Fig. 9. The steady-state photocurrent and output PCE of the devices at the maximum
for the champion cell. (For interpretation of the references to colour in this figure
power points.
legend, the reader is referred to the web version of this article.)

25
Reverse 24 17.24%
Forward x=1.0 16.92%
22
20 x=2.0
Current Density (mA cm-2)

20
x=4.0
18
15 16
15.46%
14
Count

Voc(V) Jsc(mA cm-2) FF(%) PCE(%) 12

10
Reverse 1.076 23.03 72 17.84 10
Forward 1.035 23.05 59 14.08 8

5 6
4
2
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0
13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5
Potential (V) Efficiency (%)

Fig. 10. J–V curves of the best device measured by reverse (open circuit → short Fig. 12. Histograms of the PCEs of the devices in groups of x = 1.0, x = 2.0, x = 4.0.
circuit) and forward (short circuit → open circuit) scans under AM 1.5 G illumination.

formance, resulting from a lower Jsc of 21.74 mA cm−2 , which was

3. Conclusions
ascribed to the reduced crystallinity. Fig. 9 shows the steady-state
photocurrent and output PCE of the devices in group of x = 2.0 at the
In conclusion, we have prepared high-quality CH3 NH3 PbI3 film
maximum power points with a stabilized current density output of
by increased the DMSO content in the Lewis acid-base adduct
19.79 mA cm−2 (at the voltage of 0.87 V), yielding a PCE of 17.25%.
approach to regulate the crystallization of perovskite by varied-
Fig. 10 shows the J-V curve of the best device under both reverse
stoichiometric intermediate adduct. Firstly, the degree of red
and forward bias scans, while there is a noticeable hysteresis
brown is obviously reduced, intimating more complete intermedi-
behavior. For the reverse scan, the device shows a power conver-
ate adduct CH3 NH3 I·PbI2 ·DMSO. Secondly, the time of film changed
sion efficiency (PCE) of 17.84%, with open-circuit voltage (Voc) of
turbid delays, the window period of the washing process is broaden.
1.076 V, short-circuit current density (Jsc) of 23.03 mA cm−2 , and
Thirdly, the morphology and crystallization of perovskite films can
fill factor (FF) of 0.72. For the forward scan, the device shows a
be fine-adjusted by tuning the content of DMSO. Furthermore,
PCE of 14.08%, with Voc of 1.035 V, Jsc of 23.05 mA cm−2 , and FF
the devices prepared by the precursor solution of PbI2 : CH3 NH3 I:
of 0.59. Fig. 11 shows the incident-photon-to-current conversion
xDMSO (x = 2.0) exhibit high reproducibility and the best efficiency
efficiency (IPCE) for the best performing perovskite solar cell in
of perovskite solar cells is 17.84% under one-sun illumination.
group of x = 2.0. IPCE reaches peak values of near 90% in the short-
wavelength region of the visible spectrum. The integrated Jsc is
calculated to be 21.20 mA cm−2 . This confirms that any mismatch
between the simulated sunlight and the AM1.5 G standard is neg- Acknowledgements
ligibly small [5].
Statistic results of the cell performance are provided in Fig. 12 as The authors acknowledge the financial joint support by the
histogram charts. It can be found that the devices in group of x = 2.0 National Natural Science Foundation of China (Nos. 91422301,
show better performance and the average PCE is 17.24%. Mean- 51472094, 61474047, 21301060, 61306077, U1205112), and the
while, the histogram chart demonstrates the high reproducibility Cultivation Program for Postgraduate in scientific Research Inno-
of the devices (Each team is calculated from a batch of 50 cells). vation Ability of Huaqiao University (No. 1400102002).
 Y. Tu et al. / Applied Surface Science 403 (2017) 572–577
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2017.01.
240.
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