materials

Article
Highly Efficient and Stable MAPbI3 Perovskite Solar
Cell Induced by Regulated Nucleation and
Ostwald Recrystallization
Zhen Huang 1 , Duofa Wang 1, * ID
, Song Wang 2 and Tianjin Zhang 1, *
1 Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education
Key Laboratory of Green Preparation and Application for Materials, Hubei Provincial Key Laboratory of
Polymers, Department of Materials Science and Engineering, Hubei University, Wuhan 430062, Hubei,
China; [email protected]
2 Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices, Hubei University of Arts
and Science, Xiangyang 441053, Hubei, China; [email protected]
* Correspondence: [email protected] (D.W.); [email protected] (T.Z.);
Tel.: +86-27-8866-1729 (D.W.); +86-27-8866-1729 (T.Z.)




Received: 22 April 2018; Accepted: 8 May 2018; Published: 11 May 2018


Abstract: Perovskite solar cells have attracted great attention in recent years, due to their high
conversion efficiency and solution-processable fabrication. However, most of the solar cells with
high efficiency in the literature are prepared employing TiO2 as electron transport material, which
needs sintering at a temperature higher than 450 ◦ C, and is not applicable to flexible device and
low-cost fabrication. Herein, the MAPbI3 perovskite solar cells are fabricated at a low temperature of
150 ◦ C with SnO2 as the electron transport layer. By dropping the antisolvent of ethyl acetate
onto the perovskite precursor films during the spin coating process, compact MAPbI3 films
without pinholes are obtained. The addition of ethyl acetate is found to play an important role
in regulating the nucleation, which subsequently improves the compactness of the film. The quality
of MAPbI3 films are further improved significantly through Ostwald recrystallization by optimizing
the thermal treatment. The crystallinity is enhanced, the grain size is enlarged, and the defect
density is reduced. Accordingly, the prepared MAPbI3 perovskite solar cell exhibits a record-high
conversion efficiency, outstanding reproducibility, and stability, owing to the reduced electron
recombination. The average and best efficiency reaches 19.2% and 20.3%, respectively. The device
without encapsulation maintains 94% of the original efficiency after storage in ambient air for 600 h.

Keywords: perovskite solar cell; SnO2 ; low temperature; nucleation; antisolvent; recrystallization

1. Introduction
Perovskite solar cells have attracted significant attention, due to their ability to exhibit efficient
bipolar transport, tunable direct band gaps, high solar-to-electric power conversion efficiency (PCE),
and solution process fabrication. The efficiency of these devices has also increased in recent years, from
3.8% to 22.1%, which makes it highly possible they could come into commercial mass production in
the near future [1–4]. The typical perovskite solar cell is in the structure of fluorine-doped SnO2 (FTO)
glass/electron transport layer (ETL)/perovskite/hole transport layer (HTL)/anode. Up to now, the
most successful ETL is TiO2 , and most of the highly efficient perovskite solar cells are TiO2 based [5,6].
Although TiO2 is the most widely used ETL for PSCs, the mobility (0.1–1 cm2 V−1 s−1 ) is even lower
than that of CH3 NH3 PbI3 (MAPbI3 , 20–30 cm2 V−1 s−1 ), making it not an ideal ETL material [7,8].
Moreover, the sintering temperatures for fabricating TiO2 ETL are very high (>450 ◦ C), which is a
barrier to the low-cost and stretchable device fabrication. Therefore, searching for other efficient ETLs

Materials 2018, 11, 778; doi:10.3390/ma11050778 www.mdpi.com/journal/materials

Materials 2018, 11, 778 2 of 12

is an important topic. Recently, ZnO [9], ZnAlO [10], SnO2 [11], and their composites with graphene
have been reported as ETLs for perovskite solar cell [12]. Among the ETL materials above, SnO2 is
very promising, because electron mobility is about 100–200 cm2 V−1 s−1 , and it can also be fabricated
at a temperature of 150 ◦ C [13]. However, the PCE of these devices, including SnO2 based, is still much
lower compared with those that are TiO2 based.
Very recently, it was reported that antisolvent engineering was an effective means to boost the
PCE of solar cells [14,15]. The non-polar antisolvent does not dissolve perovskite precursor (PbI2
and CH3 NH3 I), but is quite miscible with DMF. It can remove the residual solvents of DMF rapidly,
and boost the nucleation of the perovskite, which subsequently promotes the crystallization of the
perovskite film [15]. Up to now, diethyl ether, chlorobenzene, and ethyl acetate (EA) have been
selected as antisolvents in the literature [16–18]. Grätzel group employed a simple vacuum-flash
solution processing method, and obtained shiny, smooth, and crystalline perovskite films and
meso-structured TiO2 /perovskite solar cells with a PCE of 19.6% [19]. Park employed diethyl ether as
antisolvent during spin coating, which could extract the solvent quickly and promote the nucleation
of the film, leading to an efficient TiO2 /perovskite solar cell [15]. Different from the dropping
method of addition of the antisolvent, Padture utilized an antisolvent bath method by dipping the
substrate in the solution of diethyl ether, and achieved dense and crystalline perovskite film [20].
The antisolvent treatment is effective in promoting the nucleation and producing compact film, which
is successful in obtaining efficient perovskite solar cells. However, the grain size of perovskite film
prepared with antisolvent treatment is small compared with the traditional method [21], owing
to the accelerated nucleation. Accordingly, there exists more grain boundaries in the film, which
are recombination centers deteriorating the photovoltaic performance of the solar cell. Therefore,
investigations on how to enlarge the grain size and improve the crystal quality of perovskite film is
necessary to further enhance the PCE.
Here, MAPbI3 perovskite solar cells were fabricated at a low temperature of 150 ◦ C, with SnO2
as ETL. By precise control of the nucleation with antisolvent technique and subsequent promotion of
the crystallinity through Ostwald recrystallization, high quality perovskite films were obtained with
uniform thickness, smooth surface, and high compactness. Consequently, the MAPbI3 perovskite solar
cell exhibits a record-high PCE of 20.3%, with high stability and reproducibility.

2. Materials and Methods

Lead iodide (PbI2 , 99.9%, from Yingkou Youxuan Trade Co., Ltd., Yingkou, Liaoning Province,
China), CH3 NH3 I (MAI, ≥99.5%, from Xi’an Polymer Light Technology Corp, Xi’an, Shanxi
Province, China), N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO), 2,20 ,7,70 -tetrakis
[N,N-di(4-methoxyphenyl)amino]-9,90 -spirobifluorene (spiro-OMeTAD), and (6,6)-phenyl C61 butyric
acid methyl ester (PCBM) were purchased from Sigma-Aldrich (St. Louis, MO, USA), and used as
received. The SnO2 colloid precursor was from Alfa Aesar (Ward Hill, MA, USA, 15% in H2 O colloidal
dispersion).
The etched substrates of fluorine doped SnO2 (FTO) were cleaned with deionized water, acetone,
isopropanol, and ethanol in an ultrasonic cleaner for 30 min. After being dried by the N2 flow, the
substrates were put in an ultraviolet–ozone environment for 30 min to remove organic residues.
The SnO2 colloid precursor from Alfa Aesar was diluted with water (1:3, volume ratio) to prepare
the precursor. Then, it was spin-coated onto the FTO substrate with a speed of 4000 rpm for 30 s,
and heated at 150 ◦ C for 30 min. The perovskite film was deposited over SnO2 ETL by one-step spin
coating at 1000 rpm for 10 s, followed by 3500 rpm for 20 s, with the precursor composed of PbI2 , MAI,
and DMSO (1.6 M for each) in 1 mL DMF. Ethyl acetate was dropped onto the perovskite film at the
last 10th second during the spin coating. As soon as the spin coating was finished, the sample was
moved to a hotplate and annealed for 10 min at a temperature 100–140 ◦ C. The spiro-OMeTAD in
chlorobenzene (72.3 mg/mL) solution with Li-TFSI and TBP additive was spin-coated onto the top of
Materials 2018, 11, 778 3 of 12

annealed
Materials perovskite
2018, layerREVIEW
11, x FOR PEER to prepare hole transport materials. Finally, Au electrode with a thickness of
3 of 12
80 nm was deposited by thermal evaporation.
Photocurrent
Photocurrent density–voltage
density–voltage (J–V)(J–V) curves
curves were
were acquired
acquired using
using aa Keithley
Keithley 2400 2400 (Keithley
(Keithley
Instruments,Inc.,
Instruments, Inc., Cleveland, OH, USA) source meter under AM 1.5 G one-sun illuminationprovided
Cleveland, OH, USA) source meter under AM 1.5 G one-sun illumination provided
by
by aa solar
solar simulator
simulator91192-1000
91192-1000(Newport
(Newport Corporation-Oriel
Corporation-Oriel Instruments,
Instruments, Mountain
Mountain ViewView
, CA,,USA).
CA,
USA). Each curve was generated using 60 data points. The active area of the cell
2 is
Each curve was generated using 60 data points. The active area of the cell is 0.1 cm and the scan rate is 0.1 cm 2 and the

scan rate isThe

40 mV/S. 40 incident
mV/S. The incident
photon photonefficiency
to current to current efficiency
(IPCE) (IPCE) was
was obtained usingobtained
CIMPS-S using CIMPS-S
optical system.
optical system. The morphologies of the samples were investigated with a field
The morphologies of the samples were investigated with a field emission scanning electron microscope emission scanning
electron microscopeJapan
(SEM, JSM-6700F, (SEM, JSM-6700F,
Electronics Japan Electronics
Corporation, Tokyo,Corporation,
Honshu, Japan).Tokyo,TheHonshu, Japan). The
crystal structures of
crystal
the MAPbIstructures
3 films of the
were MAPbI
assessed3 films
by were
X-ray assessed
diffraction by X-ray
(XRD, D8 diffraction
advance, (XRD,
Bruker, D8 advance,
Karlsruhe, Bruker,
Germany)
Karlsruhe,
with Cu Ka Germany)
radiationwith
(λ =Cu Ka radiation
1.54178 (λ = 1.54178
Å). Optical Å). Optical
absorption spectraabsorption spectrawith
were obtained wereaobtained
UV-3600
with a UV-3600 spectrophotometer (Shimadzu, Kyoto, Japan) over the
spectrophotometer (Shimadzu, Kyoto, Japan) over the range from 300 to 900 nm. The defect range from 300 todensity
900 nm. in
The defect density
perovskite film wasinobtained
perovskite film was obtained
by measuring by measuring
the dark current the dark (J–V)
density–voltage current of density–voltage
the electron-only
(J–V)
device of with
the electron-only device with a glass/ITO/PCBM/perovskite/PCBM/Au
a glass/ITO/PCBM/perovskite/PCBM/Au architecture.
architecture. In this device, the PCBM Inlayer
this
device, the PCBM
was deposited layer
by spin was PCBM
coating deposited by in
solution spin coating PCBM
chlorobenzene. The solution
perovskite inlayer
chlorobenzene.
and Au electrodeThe
perovskite layer and Au electrode were prepared as
were prepared as the same process as the solar cell fabrication. the same process as the solar cell fabrication.

3.3.Results
Resultsand
andDiscussion
Discussion

3.1.Regulated
3.1. RegulatedNucleation
Nucleationby
byAnti-Solvent
Anti-SolventEngineering
Engineering
Thecrystal
The crystalstructure
structureof of the
the SnO
SnO22ETL
ETLwas
wascharacterized
characterizedby byX-ray
X-raydiffraction,
diffraction,performed
performedon onthe
the
film
film deposited on glass without FTO conducting layer. As shown in Figure 1a, all the
on glass without FTO conducting layer. As shown in Figure 1a, all the diffraction diffraction peaks
are indexable
peaks to the tetragonal
are indexable SnO2 structure
to the tetragonal SnO2 (space group
structure P42/mnm),
(space indicating the
group P42/mnm), formation
indicating of
the
pure SnO crystals. Transmission spectrum characterization in Figure 1b reveals
formation2of pure SnO2 crystals. Transmission spectrum characterization in Figure 1b reveals that the SnO ETL
2 that is
extremely
the SnO2 ETLtransparent.
is extremelyThetransparent.
transmittanceTheoftransmittance
the SnO2 film of deposited
the SnO2on FTO
film glass is comparable
deposited on FTO glasswith
is
bare FTO glass,
comparable withmuch
bare better than that
FTO glass, of the
much conventionally
better than that ofused TiO2 ETL. The high
the conventionally usedtransmittance
TiO2 ETL. The of
SnO minimizes the loss of photons before reaching the perovskite active layer, and improves
high 2transmittance of SnO2 minimizes the loss of photons before reaching the perovskite active layer, the light
absorption
and improvesin the light
activeabsorption
layer wheninthethesample is back
active layer incident.
when the sample is back incident.

Figure
Figure1.1.(a)
(a)X-ray
X-raydiffraction
diffractionpattern
patternof
ofSnO
SnO22film;
film;(b)
(b)Transmittance
Transmittancespectra
spectraof
ofbare
barefluorine-doped
fluorine-doped
SnO 2 (FTO) glass and TiO2, SnO2 films on FTO glass.
SnO2 (FTO) glass and TiO2 , SnO2 films on FTO glass.

The perovskite film was prepared by spin coating MAPbI3 precursor containing DMSO onto the
The perovskite film was prepared by spin coating MAPbI precursor containing DMSO onto
top of the compact SnO2 ETL, as described in the experimental 3section. The antisolvent of EA was
the top of the compact SnO2 ETL, as described in the experimental section. The antisolvent of
dropped onto the perovskite film at the last tenth of a second during the high-speed spinning stage.
EA was dropped onto the perovskite film at the last tenth of a second during the high-speed
We observed that the application of EA treatment influenced considerably the formation of
spinning stage. We observed that the application of EA treatment influenced considerably the formation
perovskite film. A smooth and transparent film was formed quickly after the dropping of EA, as
of perovskite film. A smooth and transparent film was formed quickly after the dropping of EA, as
shown in the video (Supplementary Materials, Video S1). This transparent film is indicative of the
shown in the video (Supplementary Materials, Video S1). This transparent film is indicative of the
formation of a Lewis adduct with the composition of DMSO–PbI2–CH3NH3I, as revealed in previous
formation of a Lewis adduct with the composition of DMSO–PbI2 –CH3 NH3 I, as revealed in previous
reports by Fourier transform infrared spectrometer and XRD [15]. As soon as the spin coating step
was done, the sample was placed on a hotplate, and annealed at a temperature of 100 °C. It was seen
that a dark brown perovskite film was formed after several minutes annealing. The surface of the
film is ultra-smooth, and specular reflection is obviously observed, as shown in Figure 2a and in
Materials 2018, 11, 778 4 of 12

reports by Fourier transform infrared spectrometer and XRD [15]. As soon as the spin coating step
was done, the sample was placed on a hotplate, and annealed at a temperature of 100 ◦ C. It was seen
Materials 2018,brown
that a dark 11, x FOR PEER REVIEW
perovskite 4 of
film was formed after several minutes annealing. The surface of the 12
film
is ultra-smooth, and specular reflection is obviously observed, as shown in Figure 2a and in Video S1
Video S1 in the Supporting Information. Whereas, the as-deposited film without EA treatment is
in the Supporting Information. Whereas, the as-deposited film without EA treatment is rough, gray,
rough, gray, and semitransparent, as shown in Figure 2b and in Video S2 in the Supporting
and semitransparent, as shown in Figure 2b and in Video S2 in the Supporting Information. Moreover,
Information. Moreover, the time consumed to form perovskite film is much longer in the case
the time consumed to form perovskite film is much longer in the case without EA treatment.
without EA treatment.

Figure 2. Photograph of MAPbI3 perovskite films fabricated with (a) and without (b) ethyl acetate
Figure 2. Photograph of MAPbI3 perovskite films fabricated with (a) and without (b) ethyl acetate (EA)
(EA) treatment; Top-view SEM images of MAPbI3 films with (c) and without (d) EA treatment, insets
treatment; Top-view SEM images of MAPbI3 films with (c) and without (d) EA treatment, insets are the
are the corresponding cross-sectional SEM images; (e) Schematic illustration of nucleation and
corresponding cross-sectional SEM images; (e) Schematic illustration of nucleation and crystallization
crystallization of perovskite film without/with EA treatment.
of perovskite film without/with EA treatment.

Scanning electron microscopy (SEM) was employed to investigate the effect of EA treatment on
Scanning electron
the microstructure microscopy
of the (SEM)
perovskite film.was
Asemployed
shown intoFigure
investigate
2c,d, the
theeffect of EA between
difference treatmenttheon
the microstructure
MAPbI of the perovskite film. As shown in Figure 2c,d, the difference between the MAPbI3
3 perovskite films without and with EA treatment is stark. The conventional one-step solution
perovskite films without and with EA
deposition without EA treatment treatment
induces is stark.
typical The conventional
branchlike crystals, and one-step
the SnO solution deposition
2 ETL is not fully
without EA treatment induces typical branchlike crystals, and
covered. Whereas, homogeneous perovskite film without pinholes is formed the SnO 2 ETL is not fully covered.
with the EA treatment,
Whereas, the
covering homogeneous perovskite film
SnO2 ETL completely. Thewithout pinholesSEM
cross-sectional is formed
images with
in the
the EA treatment,
insets reveals covering
that the
the SnO
perovskite ETL completely. The cross-sectional SEM images in the insets reveals
2 film with EA treatment is extremely uniform and highly dense, which is comparable that the perovskite to
filmfilm
the withquality
EA treatment
obtainedisbyextremely uniform method
vapor deposition and highly[22].dense,
Whereas, which
big is comparable
voids to the
exist in the film
sample
quality obtained
without by vapor
EA treatment and deposition method
extend to the whole[22].
depthWhereas, big voids
of perovskite exist
layer (seeininset
the sample
of Figurewithout EA
2d). The
treatment and extend to the whole depth of perovskite layer (see inset of Figure
improved morphology of the perovskite film by the antisolvent EA is ascribed to the uniform 2d). The improved
nucleation and crystallization, as illustrated by the scheme in Figure 2e. The non-polar EA does not
dissolve perovskite precursor (PbI2 and CH3NH3I) but is quite miscible with DMF. Therefore, it can
remove the residual solvents of DMF rapidly and boost the nucleation of the perovskite.
Subsequently, an abundance of nuclei is formed and uniformly distributed on the substrate, which
grow into uniform grains and ultimately coalesce into a dense polycrystalline film under thermal
Materials 2018, 11, 778 5 of 12

morphology of the perovskite film by the antisolvent EA is ascribed to the uniform nucleation and
crystallization, as illustrated by the scheme in Figure 2e. The non-polar EA does not dissolve perovskite
precursor (PbI2 and CH3 NH3 I) but is quite miscible with DMF. Therefore, it can remove the residual
solvents of DMF rapidly and boost the nucleation of the perovskite. Subsequently, an abundance
Materials 2018, 11, x FOR PEER REVIEW
of
5 of 12
nuclei is formed and uniformly distributed on the substrate, which grow into uniform grains and
ultimately coalesce
annealing, into a dense
as illustrated in Figurepolycrystalline
2e. In the casefilm under
withoutthermal annealing,
EA, nuclei on the as illustrated in Figure
substrate are formed 2e.
In the case without EA, nuclei on the substrate are formed randomly,
randomly, and the number is comparably much less. The nuclei continue to grow controlled by and the number is comparably
much less.
Ostwald The nuclei
ripening undercontinue
thermal to grow controlled
annealing. by Ostwald
In this case, gaps are ripening under
easily formed thermalthe
between annealing.
grains.
In this case, gaps are easily formed between the grains.
Ultraviolet–visible light (UV-vis) absorption spectra of the films with/without EA treatment are
Ultraviolet–visible
compared in Figure 3a. light The (UV-vis)
absorption absorption
edges forspectra of the films
both spectra with/without
are close to 780 nm,EA treatment
which is in
are compared
agreement withinliterature
Figure 3a. The
[23]. The absorption
intensity of edges for both spectra
the absorption arethe
peak for close
filmtowith
780 nm, which is in
EA treatment is
agreement with literature [23]. The intensity of the absorption peak for
very strong. Contrarily, the intensity without EA treatment is rather weak, which is consistent with the film with EA treatment
is very
the strong. Contrarily,
photograph in Figure 2b thethat
intensity without
the sample is EA treatment is rather
semitransparent. weak, which
The inferior is consistent
absorption for the
with the photograph
untreated one is ascribed in Figure
to the low 2b that the sample
compactness is semitransparent.
of the perovskite film, inThe whichinferior
the FTOabsorption
glass is notfor
the untreated one is ascribed to the low compactness of the perovskite film,
fully covered, as shown in Figure 2. The crystallinity of the MAPbI3 films is characterized by X-ray in which the FTO glass
is not fully pattern
diffraction covered,and as shown
shownininFigure Figure2. 3b.
The Allcrystallinity of the MAPbI
the diffraction films is characterized
peaks 3corresponding to the
by X-ray diffraction pattern and shown in Figure 3b. All the diffraction
orthorhombic MAPbI3 are indexed in the pattern. No obvious difference in the position of the peaks corresponding to
the orthorhombic MAPbI
diffraction peaks is observed are indexed in the pattern. No obvious difference
3 for the MAPbI3 films with/without EA treatment. The full width at half in the position of the
diffraction (FWHM)
maximum peaks is observed
of the (110) for diffraction
the MAPbI3peak filmsofwith/without
MAPbI3 film,EA treatment.
without and with The full width at half
EA treatment, is
maximum (FWHM) of the (110) diffraction peak of MAPbI film, without and
0.088 and 0.115, respectively. It reveals that the grain size of3 the non-treated sample is larger, which with EA treatment, is
0.088
is and 0.115,
consistent with respectively.
SEM results. It reveals
Moreover, thatan
theadditional
grain sizediffraction
of the non-treated
peak at sample
12.65° isisobserved
larger, whichin the is
consistent with ◦
XRD pattern of SEM results. Moreover,
the non-treated sample,an additional
which diffraction
corresponds peak
to the at 12.65
(001) plane is ofobserved in the XRD
PbI2. However, it is
patternfor
absent of the MAPbI
non-treated3 filmsample,
with EAwhich corresponds
treatment. to the (001)
This indicates that plane of PbI2 .of
employment However,
antisolventit isEAabsent
not
for the
only MAPbI3the
improves film with EA treatment.
compactness of the film,Thisbutindicates that employment
also promotes of antisolvent
the conversion of PbI2 toEA not only
perovskite
improves
MAPbI 3. the compactness of the film, but also promotes the conversion of PbI2 to perovskite MAPbI3 .

Figure
Figure 3.
3. (a) UV-visabsorption
(a) UV-vis absorptionspectra
spectraand
and(b)
(b) XRD
XRD pattern
pattern of the
of the MAPbI
MAPbI 3 perovskite without/with
3 perovskite without/with EA
EA
treatment. The heart and dot denote diffraction peaks corresponding to PbI2 andtoFTO
treatment. The heart and dot denote diffraction peaks corresponding 2 and FTO films,
PbIfilms, respectively.
respectively.

3.2. Improved Quality of Perovskite Film by Ostwald Recrystallization

3.2. Improved Quality of Perovskite Film by Ostwald Recrystallization
In the literature regarding work on antisolvent assisted fabrication, the MAPbI3 perovskite
In the literature regarding work on antisolvent assisted fabrication, the MAPbI3 perovskite films
films were mostly annealed at 100 ◦ C, which was the optimized temperature for the traditional
were mostly annealed at 100 °C, which was the optimized temperature for the traditional fabrication
fabrication method. However, the nucleation and crystallization dynamics are different when
method. However, the nucleation and crystallization dynamics are different when antisolvent is
antisolvent is employed. Therefore, we investigate the effect of annealing temperature on the
employed. Therefore, we investigate the effect of annealing temperature on the morphology and
morphology and crystallinity of the perovskite film, to improve the crystal quality of the perovskite film.
crystallinity of the perovskite film, to improve the crystal quality of the perovskite film. Figure 4 is
Figure 4 is the SEM images of the perovskite film annealed at different temperatures. As shown,
the SEM images of the perovskite film annealed at different temperatures. As shown, the
the crystallinity is significantly improved with the increase of temperature. The average grain
crystallinity is significantly improved with the increase of temperature. The average grain size◦ is
size is increased from 150 to 500 nm when the temperature is increased from 100 to 130 C.
increased from 150 to 500 nm when the temperature is increased from 100 to 130 °C. The surfaces of
The surfaces of the films become smoother as well. Columnar crystals with heights reaching the
the films become smoother as well. Columnar crystals with heights reaching the whole thickness of
whole thickness of the perovskite film are clearly observed, as shown in the cross-sectional SEM image
the perovskite film are clearly observed, as shown in the cross-sectional SEM image (see Figure 4g).
Further increasing the temperature to 140 °C leads to increased gaps between the grain boundaries
instead. The enlarged grain size can be explained by the Ostwald recrystallization model, as
illustrated in Figure 4h. The Ostwald ripening process is driven by the surface energy, and normally
involves two coupled steps. The first step is the dissolution of small-sized crystals, because of the
higher equilibrium vapor pressure (process ① in Figure 4h); the second step is the formation of
Materials 2018, 11, 778 6 of 12

(see Figure 4g). Further increasing the temperature to 140 ◦ C leads to increased gaps between the
grain boundaries instead. The enlarged grain size can be explained by the Ostwald recrystallization
model, as illustrated in Figure 4h. The Ostwald ripening process is driven by the surface energy,
and normally involves two coupled steps. The first step is the dissolution of small-sized crystals,
because of the higher equilibrium vapor pressure (process 1 in Figure 4h); the second step is the
Materials 2018, 11, x FOR PEER REVIEW 6 of 12
formation of large-sized crystals to decrease the surface energy (process 2 in Figure 4h). At higher
temperatures, more small-sized crystal are dissolved and recrystallized to form larger-size crystals,
more small-sized crystal are dissolved and recrystallized to form larger-size crystals, leading to
leading to improved film quality.
improved film quality.

Figure 4.
Figure 4. SEM
SEMimages
imagesofofperovskite
perovskitefilms annealed
films (a) (a)
annealed 100100
°C; (b)
◦ C;110
(b) °C;
110(c) 120(c)°C;
◦ C; (d)130
120 °C; (e) 140
◦ C; (d)130 ◦ C;

(e) 140 C; (f) Cross-sectional SEM images of the perovskite films annealed at (f) 100 C and (g) 130 ◦(h)
°C; (f) Cross-sectional
◦ SEM images of the perovskite films annealed at (f) 100 °C and
◦ (g) 130 °C; C;
Illustration
(h) of Ostwald
Illustration recrystallization
of Ostwald recrystallizationprocess.
process.

The XRD patters and UV–vis absorption spectra of the MAPbI3 films annealed at different
The XRD patters and UV–vis absorption spectra of the MAPbI3 films annealed at different
temperatures are measured and shown in Figure 5. As seen, orthorhombic perovskite MAPbI3 films
temperatures are measured and shown in Figure 5. As seen, orthorhombic perovskite MAPbI3 films
are formed at all temperatures. The intensity of diffraction peaks is increased and the full width at
are formed at all temperatures. The intensity of diffraction peaks is increased and the full width at
half maximum is decreased, with the increase of temperature, indicating the enhancement of the
half maximum is decreased, with the increase of temperature, indicating the enhancement of the
crystallinity. When the temperature reaches 140 °C, a diffraction peak corresponding to PbI2 at 12.65°
is observed. It is ascribed to be induced by the decomposition of MAPbI3, since it only appears at the
highest temperature. In the UV-vis absorption spectra, no distinct difference is observed among the
samples prepared at different temperatures, indicating that all perovskite films show similar
absorption efficiency.
Materials 2018, 11, 778 7 of 12

crystallinity. When the temperature reaches 140 ◦ C, a diffraction peak corresponding to PbI2 at 12.65◦
is observed. It is ascribed to be induced by the decomposition of MAPbI3 , since it only appears at
the highest temperature. In the UV-vis absorption spectra, no distinct difference is observed among
the samples prepared at different temperatures, indicating that all perovskite films show similar
absorption
Materials 2018,efficiency.
11, x FOR PEER REVIEW 7 of 12

Figure 5.5. (a)

Figure (a) XRD
XRD patterns
patterns and
and (b)
(b) UV-vis
UV-vis absorption
absorption spectra
spectra of
of the
the perovskite
perovskite films
films annealed
annealed at
at
different temperatures. The heart and club denote diffraction peaks corresponding to
different temperatures. The heart and club denote diffraction peaks corresponding to PbI2 and PbI2 and

MAPbI3,, respectively.
MAPbI respectively.
3

3.3. Photovoltaic
3.3. Photovoltaic Properties
Properties of
of the
the Perovskite
Perovskite Solar
SolarCell
Cell
Perovskitesolar
Perovskite solarcells
cellswithwithaastructure
structureofofFTO/SnO
FTO/SnO/MAPbI 2/MAPbI3/Spiro-OMeTAD/Au are fabricated,
2 3 /Spiro-OMeTAD/Au are fabricated,
and the photovoltaic performance measured under AM 1.5AM
and the photovoltaic performance measured under 1.5 simulated
simulated solar illumination
solar illumination (100 mW/cm (100
2 ).
mW/cm 2). It is found that the perovskite solar cell prepared at 130 °C
It is found that the perovskite solar cell prepared at 130 ◦ C exhibits the highest PCE, which is consistent exhibits the highest PCE, which
is consistent
with the SEM and withXRD theresults
SEM that and itXRDmaintainsresults thethat
highestit maintains
crystallinity theand highest crystallinity
compactness. Figureand 6a
compactness. Figure 6a plots the J–V curve of the perovskite ◦
plots the J–V curve of the perovskite cell annealed at 130 C. The PCE is 19.24 ± 1.06% (the best cell annealed at 130 °C. The PCE is 19.24
PCE
± 1.06% 20.3%)
reaches (the best inPCE reaches scan,
the reverse 20.3%)and in the
17.2reverse
± 0.81% scan,
(the andbest17.2
PCE ± 0.81% (the best
is 18.01%) PCEforward
in the is 18.01%) scan. in
the forward scan. Due to the relatively larger bandgap of MAPbI
Due to the relatively larger bandgap of MAPbI3 (1.55 eV) compared to FAPbI3 (1.48 eV), the PCE 3 (1.55 eV) compared to FAPbI3 (1.48

eV),
is the PCE
slightly loweris slightly
than the lower than the formanidinium
formanidinium lead trihalidelead trihalide
(FAPbI (FAPbI3) solar cell reported by
3 ) solar cell reported by You group
You group
(20.5%) [24].(20.5%)
However, [24].
thisHowever, this is
is the record PCEthevalue
record forPCEMAPbI valueperovskite
for MAPbI 3 perovskite solar cell with
solar cell with SnO2 ETL, as
3
SnO 2 ETL, as far as we know. A summary of the perovskite solar cell based on SnO2 ETL with PCE
far as we know. A summary of the perovskite solar cell based on SnO2 ETL with PCE higher than 15%
higher
in literaturethanis 15%shown ininliterature
Table 1. Inisthe shown
typicalinincident
Table 1. In the typical incident
photon-to-electron conversion photon-to-electron
efficiency (IPCE)
conversion efficiency (IPCE) plot in Figure 6b, rather
plot in Figure 6b, rather high values are achieved, and the highest reaches 97% in the high values are achieved, and the highest
visible region.
reaches 97% in the visible region. The integrated short-circuit
2
The integrated short-circuit current is 23.76 mA/cm and matches well with the J–V results. Moreover, current is 23.76 mA/cm 2 and matches

wellcell
the withshowsthe J–Vvery results.
stableMoreover,
output current the cell showsand
density very PCEstable
at theoutput
maximal currentpowerdensity
point, and asPCE
shown at the
in
maximal power point, as shown in Figure 6c. It delivers stabilized
Figure 6c. It delivers stabilized current density of 21.45 mA/cm and PCE of 19.57% at 0.913V, which 2 current density of 21.45 mA/cm 2

and
is PCE of 19.57%
comparable to the at 0.913V,
values whichfrom
obtained is comparable
the J–V scan. to the
Thevalues
stability obtained
measurementfrom the J–V solar
of the scan.cells
The
stabilityencapsulation
without measurement isofperformed the solar cells withoutthe
by storing encapsulation
device in theislab performed
(30% humidity,by storing
under thelaboratory
device in
the lab (30% humidity, under laboratory light illumination)
light illumination) and measuring the PCE every 60 h. As shown in Figure 6d, the solar cell exhibitsand measuring the PCE every 60 h. As
shown in Figure 6d, the solar cell exhibits high stability, the
high stability, the Jsc is nearly unchanged, the Voc decreased from 1.08 V to 1.06 V, the FF decreased Jsc is nearly unchanged, the Voc
decreased
from 76% tofrom 72%,1.08 andVthe to efficiency
1.06 V, the FF decreased
decreased from 76%
from 19.57% to 72%,(94%
to 18.35% and of thethe
efficiency
initial value)decreased
after
from
600 h. 19.57% to 18.35% (94% of the initial value) after 600 h.
Toinvestigate
To investigatethe theeffect
effectof ofannealing
annealingtemperature
temperatureon onthethephotovoltaic
photovoltaic performance
performance of of the
the solar
solar
cell and to reveal the mechanism, we compared the photovoltaic
cell and to reveal the mechanism, we compared the photovoltaic characteristics and the distribution characteristics and the distribution
of the
of the solar
solar cells
cells annealed
annealed at at 100
100 and
and 130130 °C.◦ C.AsAsshown
shownininFigure Figure7a, 7a,thethecells
cellsexhibit
exhibit similar
similar Jsc.Jsc.
It
Itindicates
indicatesthat thatthe
thetwo twoMAPbI
MAPbI3 3filmsfilmsmaintain
maintainsimilar
similarlight lightabsorption
absorption efficiency
efficiency since
since it is the
it is the most
most
important factor affecting Jsc. This is consistent with the UV-vis results in Figure 5. In Figures 7b andand
important factor affecting Jsc. This is consistent with the UV-vis results in Figure 5. In Figure 7b 7c,
Figure
an obvious 7c, an obvious
increase in Vocincrease
and FFinisVoc and FFwhen
observed is observed when the
the temperature temperature
is increased. is increased.
It reveals that theIt
reveals that the
recombination raterecombination
of electrons israte lower of inelectrons
the cell of is 130
lower ◦ C,in the cell
which leads of to130
the°C, which
higher PCE, leads to the
as shown
higher PCE, as shown in Figure 7d. The lower recombination rate can be ascribed to the improved
crystallinity by high temperature annealing. When the annealing temperature is increased to 130 °C,
abundant grain boundaries disappear, and accordingly, the defect density is reduced, leading to the
increased lifetime and decreased recombination rate of electrons.
Materials 2018, 11, 778 8 of 12

in Figure 7d. The lower recombination rate can be ascribed to the improved crystallinity by high
temperature annealing. When the annealing temperature is increased to 130 ◦ C, abundant grain
boundaries disappear, and accordingly, the defect density is reduced, leading to the increased lifetime
Materials
and 2018, 11, xrecombination
decreased FOR PEER REVIEW
rate of electrons. 8 of 12

Figure 6.
Figure 6. (a)
(a) J–V;
J–V; (b)
(b) Incident
Incident photon
photon to
to current
current efficiency
efficiency (IPCE;
(IPCE; black)
black) and
and integrated
integrated short-circuit
short-circuit
current density
current density (blue)
(blue) ofof the
the solar
solar cell
cell annealed
annealed atat 130
130 ◦°C; (c) The
C; (c) The maximal
maximal steady-state
steady-state power
power
conversion efficiency (blue) and photocurrent output (black); (d) Stability data of cell stored
conversion efficiency (blue) and photocurrent output (black); (d) Stability data of cell stored in ambient in
ambient air, inset is the J–V curves of the device, which are measured initially
air, inset is the J–V curves of the device, which are measured initially and after 600 h storage.and after 600 h
storage.
Table 1. Summary of perovskite solar cell based on SnO2 ETL with efficiency higher than 15%
Table
in 1. Summary of perovskite solar cell based on SnO2 ETL with efficiency higher than 15% in
literature.
literature.
Electron Transport Layer Perovskite Efficiency (The Best)
Electron Transport Layer Perovskite Efficiency (The Best) Ref. Ref.
SnO2 (FAPbI3 )0.97 (MAPbBr3 )0.03 20.5% [24]
SnO2 (FAPbI3)0.97(MAPbBr3)0.03 20.5% [24]
Nb/SnO2 MAPbI3 17.57 [25]
Nb/SnO 2
MgO/SnO 2
MAPbI
MAPbI33 17.57
18.82% [26] [25]
MgO/SnOmp-SnO2 2 MAPbI33
MAPbI 16.17%
18.82% [27] [26]
C60/SnO2 (invert) MAPbI3 18.8% [28]
mp-SnO 2
SnO2 /PCBM
MAPbI
MAPbI3
3 16.17%
19.45% [29]
[27]
C60/SnO2(invert)
SnO2 MAPbI
MAPbI33 18.8%
15.07% [30] [28]
SnO2/PCBM SnO2 (FAPbIMAPbI
3 )0.85 (MAPbBr
3 3 )0.15 18.4%
19.45% [31] [29]
SnO2 (FAPbI3 )0.8 (MAPbBr3 )0.2 20.8% [32]
SnO2SnO MAPbI
MAPbI33 15.07%
17.2% [33] [30]
2
SnO2SnO2 (FAPbI3)0.85 (MAPbBr
MAPbI 3 3)0.15 18.4%
18.32% [34] [31]
SnOLi/SnO
2 2 (FAPbI3)0.8MAPbI
(MAPbBr
3 3)0.2
18.2%
20.8% [35] [32]
SnO2 MAPbI3 18.16% [36]
SnO2SnO2 MAPbI
MAPbI33 17.2%
18.77% [37] [33]
SnOZnO–SnO
2 2 MAPbI
MAPbI33 18.32%
15.2% [38] [34]
Li/SnOSnO2 2
FA0.8 Cs0.2 PbI3
MAPbI3 19.57%
18.2% [39]
[35]
SnO2 MAPbI3 20.3% Our work
SnO2 MAPbI3 18.16% [36]
SnO2 MAPbI3 18.77% [37]
ZnO–SnO2 MAPbI3 15.2% [38]
SnO2 FA0.8Cs0.2PbI3 19.57% [39]
SnO2 MAPbI3 20.3% Our work
 Materials 2018,11,
Materials2018, 11,778
x FOR PEER REVIEW 99 of
of12
12

Figure 7. Statistical distribution of the photovoltaic parameters for the MAPbI3 solar cell anneal at
100 °C and 130 °C. (a) Jsc; (b) Voc; (c) fill factor; (d) PCE.

To confirm
Figure7.7.the
Figure dependence
Statistical
Statistical distribution
distributionof ofdefect
ofthe density on
thephotovoltaic
photovoltaic the annealing
parameters
parameters for
forthe temperature,
theMAPbI
MAPbI3 3solar we
solarcell
cell fabricated
anneal
anneal atat an
100 ◦ C and 130 ◦ C. (a) Jsc; (b) Voc; (c) fill factor; (d) PCE.
electron-only device
100 °C and 130 with the
°C. (a) Jsc;glass/ITO/PCBM/perovskite/PCBM/Au
(b) Voc; (c) fill factor; (d) PCE. architecture, and assessed the
trap density in these devices. The dark J–V characteristics were measured to obtain the electron trap
densities.To To confirm
confirm
Figure 8 the
thedependence
shows dependence
the typical ofofdefect
darkdensity
defect density on
onthe
theannealingof temperature,
annealing
J–V characteristics temperature,we
electron-only we fabricated
fabricated
devices an
withan the
electron-only
electron-only device
device with
with the
the glass/ITO/PCBM/perovskite/PCBM/Au
glass/ITO/PCBM/perovskite/PCBM/Au
perovskite film annealed at 100 and 130 °C. The trap densities were estimated by the space architecture,
architecture, and and assessed
assessed the
the
traptrap density
density in these
in these devices. devices.
The dark TheJ–Vdark J–V characteristics
characteristics were to
were measured measured
obtain the toelectron
obtain trap
the
charge–limited current (SCLC) model [40]. The linear region at low bias corresponds to the ohmic
electron
densities.trap densities.
Figure 8 showsFigure the8 typical
shows the darktypical dark J–V characteristics
J–V characteristics of electron-only
of electron-only devices withdevicesthe
response. The current quickly increases when the bias◦ voltage exceeds the kink point, demonstrating
with the perovskite
perovskite film annealed
film annealed at 100 and at 100130and °C.130The C. Thedensities
trap trap densities were estimated
were estimated by thebyspace
the
that the trap
space states are
charge–limited
charge–limited
completely
current current
(SCLC)(SCLC)
filled. [40].
model model
The trap-state
[40].
The
density
Theregion
linear
can be at
linearatregion
low bias
determined
low bytothe
bias corresponds
corresponds
trap-filled
the ohmicto
limit the ohmic The
response.
voltage
V
( response.
usingThe
TFL )current current
quickly
equation
V
quickly
increases
TFL when= en L2 / 2εε
increases
t the bias when
0voltage
, where L voltage
the exceeds
bias
is the
the kinkexceeds
point,the
thickness kink point,
demonstrating
of the perovskite
ε
demonstrating
that
film, by the
the trap
is trap-filled
that
states
the relative
the
are trap states
completely are completely
filled.
dielectric constant
The
of
filled.
trap-state
the
The
density
perovskite
trap-state
can be density
determined can be
by
(taken as the value 32 for MAPbI3
determined
the trap-filled
V limit voltage (VTELV
) using equation ε
) using
TFL = en L 2
equation
t / 2 εε
VTEL = ent L2 /2εε 0 , where L is the thickness of
0 , where L is the thickness
limit voltage (
the perovskite
TFL
film, εreport
is the relative dielectric constant permittivity,
of the perovskite nt as the
(taken
of the perovskite
value 32 for
according
film, ε is the relative dielectric constant of the perovskite (takenand
to a previous [41]), 0 is the vacuum
as the is the 32
value trapfordensity.
MAPbI3The
MAPbI3 according to a previous report [41]), ε 0 is the vacuum permittivity, and n t is the trap density.
electron trap densities are calculated to εbe 9.8 × 1015 and 15 7.6 × 1015 cm15−3 forn−t 3the films annealed at 100
The electron
according totrap
a densities
previous are
report calculated
[41]), 0 to
is be
the 9.8 ×
vacuum 10 and 7.6
permittivity,× 10and cm for
is the thetrap
films annealed
density. Thethat
and 130 °C, respectively. It explains the difference of the photovoltaic performance
◦ C, respectively. very well,
atelectron
100 andtrap
130densities are It explains
calculated to be the
9.8 difference
× 10 of the photovoltaic performance
15 and 7.6 × 1015 cm−3 for the films annealed at very well,
100
the solar
that cellsolar
the annealed
cell at 130at°C
annealed 130 exhibits
◦ C exhibitshigherhigher VocVoc and
and FF,
FF, which
which isisinduced
induced by by
the the
lowerlower
and 130 °C, respectively. It explains the difference of the photovoltaic performance very well, that
recombination
recombination raterateof electrons.
of electrons.
the solar cell annealed at 130 °C exhibits higher Voc and FF, which is induced by the lower
recombination rate of electrons.

Figure 8. Dark
Figure
Figure 8.8.DarkJ–V
Dark characteristics
J–VJ–V
characteristics ofofthe
characteristics the
of theelectron
electron only
only device
only device
electron based
based on
device MAPbI
based on
on MAPbI
3 perovskite
MAPbI perovskite
3 film annealedfilm
3 perovskite film
annealed ◦
100at C
100 ◦
atannealed at°C
and and
130
100 130 130
°CC.and °C. °C.
Materials 2018, 11, 778 10 of 12

4. Conclusions
In summary, MAPbI3 perovskite solar cells with SnO2 as ETL were fabricated at a low temperature
of 150 ◦ C. Compact perovskite film without pinholes is obtained by dropping the antisolvent of ethyl
acetate onto the perovskite precursor films during the spin coating process. Because the antisolvent
(ethyl acetate) does not dissolve perovskite precursor, but is quite miscible with DMF, the addition
of antisolvent effectively extracts residual solvent (DMF), and accelerates the nucleation of MAPbI3
perovskite, which accordingly improves the compactness of the MAPbI3 films. The quality of MAPbI3
film was further improved significantly through Ostwald recrystallization process, by optimizing the
thermal treatment. The crystallinity is enhanced, the grain size is increased three times, columnar
crystals with heights reaching the whole thickness of the film are formed, and the defect density in
MAPbI3 film is reduced from 9.8 × 1015 to 7.6 × 1015 cm−3 when the annealing temperature is increased
from the widely performed temperature of 100 to 130 ◦ C. Consequently, MAPbI3 perovskite solar cell
with record-high conversion efficiency, and outstanding reproducibility and stability is achieved. The
average and best efficiency reaches 19.2% and 20.3%, respectively. The device without encapsulation
maintains 94% of the original efficiency after storage in ambient air for 600 h.

Supplementary Materials: The following are available online at https://zenodo.org/record/1246032#

.WvfxYVKSCJ0, Video S1: fabrication process of the MAPbI3 film with antisolvent treatment, Video S2: fabrication
process of the MAPbI3 film without antisolvent treatment.
Author Contributions: Z.H. and S.W. performed the experiments; D.W. and T.Z. designed this study and analyzed
the data; all authors read and approve the final manuscript.
Funding: This work has been supported by National Natural Science Foundation of China (No. 11174071,
11304088 and 51372180) and Special Technical Innovation Project of Hubei Province (No. 2016AAA035).
Acknowledgments: We thank Jinhua Li in Hubei University for the experiments on Au electrode deposition.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal halide perovskites as visible-light sensitizers
for photovoltaic cells. J. Am. Chem. Soc. 2009, 131, 6050–6051. [CrossRef] [PubMed]
2. Lee, M.M.; Teuscher, J.; Miyasaka, T.; Murakami, T.N.; Snaith, H.J. Efficient hybrid solar cells based on
meso-superstructured organometal halide perovskites. Science 2012, 338, 643–647. [CrossRef] [PubMed]
3. Jeon, N.J.; No, J.H.; Kim, Y.C.; Yang, W.S.; Ryu, S.; Seok, S.I. Solvent engineering for high-performance
inorganic-organic hybrid perovskite solar cells. Nat. Mater. 2014, 13, 897–903. [CrossRef] [PubMed]
4. Yang, W.S.; Park, B.W.; Jung, E.H.; Jeon, N.J.; Kim, Y.C.; Lee, D.U.; Shin, S.S.; Seo, J.; Kim, E.K.; Noh, J.H.
Iodide management in formamidinium-lead-halide-based perovskite layers for efficient solar cells. Science
2017, 356, 1376–1379. [CrossRef] [PubMed]
5. Son, D.Y.; Lee, J.W.; Choi, Y.J.; Jang, I.H.; Lee, S.; Yoo, P.J.; Shin, H.; Ahn, N.; Choi, M.; Kim, D.; Park, N.G.
Self-formed grain boundary healing layer for highly efficient CH3 NH3 PbI3 perovskite solar cells. Nat. Energy
2016, 1, 16081. [CrossRef]
6. Arora, N.; Dar, M.I.; Hinderhofer, A.; Pellet, N.; Schreiber, F.; Zakeeruddin, S.M.; Grätzel, M. Perovskite
solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20%. Science 2017, 358,
768–771. [CrossRef] [PubMed]
7. Breckenridge, R.G.; Hosler, W.R. Electrical Properties of Titanium Dioxide Semiconductors. Phys. Rev. 1953,
91, 793–802. [CrossRef]
8. Ponseca, C.S., Jr.; Savenije, T.J.; Abdellah, M.; Zheng, K.; Yartsev, A.; Pascher, T.; Harlang, T.; Chabera, P.;
Pullerits, T.; Stepanov, A.; et al. Organometal halide perovskite solar cell materials rationalized: Ultrafast
charge generation, high and microsecond-long balanced mobilities, and slow recombination. J. Am. Chem. Soc.
2014, 136, 5189–5192. [CrossRef] [PubMed]
9. Liu, D.; Kelly, T.L. Perovskite solar cells with a planar heterojunction structure prepared using
room-temperature solution processing techniques. Nat. Photonics 2014, 8, 133–138. [CrossRef]
Materials 2018, 11, 778 11 of 12

10. Mahmood, K.; Swain, B.S.; Jung, H.S. Controlling the surface nanostructure of ZnO and Al-doped ZnO thin
films using electrostatic spraying for their application in 12% efficient perovskite solar cells. Nanoscale 2014,
6, 9127–9138. [CrossRef] [PubMed]
11. Song, S.; Kang, G.; Pyeon, L.; Lim, C.; Lee, G.Y.; Park, T.; Choi, J. Systematically Optimized Bilayered Electron
Transport Layer for Highly Efficient Planar Perovskite Solar Cells (η = 21.1%). ACS Energy Lett. 2017, 2,
2667–2673. [CrossRef]
12. Zhu, Z.; Ma, J.; Wang, Z.; Mu, C.; Fan, Z.; Du, L.; Bai, Y.; Fan, L.; Yan, H.; Phillips, D.L.; et al. Efficiency
enhancement of perovskite solar cells through fast electron extraction: The role of graphene quantum dots.
J. Am. Chem. Soc. 2014, 136, 3760–3763. [CrossRef] [PubMed]
13. Rao, H.S.; Chen, B.X.; Li, W.G.; Xu, Y.F.; Chen, H.Y.; Kuang, D.B.; Su, C.Y. Improving the Extraction
of Photogenerated Electrons with SnO2 Nanocolloids for Efficient Planar Perovskite Solar Cells.
Adv. Funct. Mater. 2015, 25, 7200–7207. [CrossRef]
14. Konstantakou, M.; Perganti, D.; Falaras, P.; Stergiopoulos, T. Anti-Solvent Crystallization Strategies for
Highly Efficient Perovskite Solar Cells. Crystals 2017, 7, 291–312. [CrossRef]
15. Ahn, N.; Son, D.Y.; Jang, I.H.; Kang, S.M.; Choi, M.; Park, N.G. Highly Reproducible Perovskite Solar Cells
with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II)
Iodide. J. Am. Chem. Soc. 2015, 137, 8696–8699. [CrossRef] [PubMed]
16. Gao, Y.; Yang, L.; Wang, F.; Sui, Y.; Sun, Y.; Wei, M.; Cao, J.; Liu, H. Anti-solvent surface engineering
via diethyl ether to enhance the photovoltaic conversion efficiency of perovskite solar cells to 18.76%.
Superlattices Microstruct. 2018, 113, 761–768. [CrossRef]
17. Yoon, S.; Ha, M.W.; Kang, D.W. PCBM-blended chlorobenzene hybrid anti-solvent engineering for efficient
planar perovskite solar cells. J. Mater. Chem. C 2017, 5, 10143–10151. [CrossRef]
18. Troughton, J.; Hooper, K.; Watson, T.M. Humidity Resistant Fabrication of CH3 NH3 PbI3 Perovskite Solar
Cells and Modules. Nano Energy 2017, 39, 60–68. [CrossRef]
19. Li, X.; Bi, D.; Yi, C.; Décoppet, J.D.; Luo, J.; Zakeeruddin, S.M.; Hagfeldt, A.; Grätzel, M. A vacuum
flash-assisted solution process for high-efficiency large-area perovskite solar cells. Science 2016, 353,
8060–8068. [CrossRef] [PubMed]
20. Zhou, Y.; Yang, M.; Wu, W.; Vasiliev, A.L.; Zhu, K.; Padture, N.P. Room-temperature crystallization of
hybrid-perovskite thin films via solvent–solvent extraction for high-performance solar cells. J. Mater. Chem. A
2015, 3, 8178–8184. [CrossRef]
21. Wang, Y.; Wu, J.; Zhang, P.; Liu, D.; Zhang, T.; Ji, L.; Gu, X.; Chen, Z.D.; Li, S. Stitching triple cation perovskite
by a mixed anti-solvent process for high performance perovskite solar cells. Nano Energy 2017, 39, 616–625.
[CrossRef]
22. Liu, M.; Johnston, M.B.; Snaith, H.J. Efficient planar heterojunction perovskite solar cells by vapour
deposition. Nature 2013, 501, 395–399. [CrossRef] [PubMed]
23. Tidhar, Y.; Edri, E.; Weissman, H.; Zohar, D.; Hodes, G.; Cahen, D.; Rybtchinski, B.; Kirmayer, S.
Crystallization of methyl ammonium lead halide perovskites: Implications for photovoltaic applications.
J. Am. Chem. Soc. 2014, 136, 13249–13256. [CrossRef] [PubMed]
24. Jiang, Q.; Zhang, L.; Wang, H.; Yang, X.; Meng, J.; Liu, H.; Yin, Z.; Wu, J.; Zhang, X.; You, J. Enhanced
electron extraction using SnO2 for high-efficiency planar-structure HC(NH2 )2 PbI3 -based perovskite solar
cells. Nat. Energy 2016, 2, 16177–16184. [CrossRef]
25. Ren, X.; Yang, D.; Yang, Z.; Feng, J.; Zhu, X.; Niu, J.; Liu, Y.; Zhao, W.; Liu, S.F. Solution-Processed Nb:SnO2
Electron Transport Layer for Efficient Planar Perovskite Solar Cells. ACS Appl. Mater. Interfaces 2017, 9,
2421–2429. [CrossRef] [PubMed]
26. Ma, J.; Yang, G.; Qin, M.; Zheng, X.; Lei, H.; Chen, C.; Chen, Z.; Guo, Y.; Han, H.; Zhao, X.; et al. MgO
Nanoparticle Modified Anode for Highly Efficient SnO2 -Based Planar Perovskite Solar Cells. Adv. Sci. 2017,
4, 1700031–1700040. [CrossRef] [PubMed]
27. Liu, Q.; Qin, M.C.; Ke, W.J.; Zheng, X.L.; Chen, Z.; Qin, P.L.; Xiong, L.B.; Lei, H.W.; Wan, J.W.; Wen, J.; et al.
Enhanced Stability of Perovskite Solar Cells with Low-Temperature Hydrothermally Grown SnO2 Electron
Transport Layers. Adv. Funct. Mater. 2016, 26, 6069–6075. [CrossRef]
28. Zhu, Z.; Bai, Y.; Liu, X.; Chueh, C.C.; Yang, S.; Jen, A.K. Enhanced Efficiency and Stability of Inverted
Perovskite Solar Cells Using Highly Crystalline SnO2 Nanocrystals as the Robust Electron-Transporting
Layer. Adv. Mater. 2016, 28, 6478–6484. [CrossRef] [PubMed]
Materials 2018, 11, 778 12 of 12

29. Ke, W.; Xiao, C.; Wang, C.; Saparov, B.; Duan, H.S.; Zhao, D.; Xiao, Z.; Schulz, P.; Harvey, S.P.; Liao, W.;
et al. Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar
Perovskite Solar Cells. Adv. Mater. 2016, 28, 5214–5221. [CrossRef] [PubMed]
30. Duan, J.; Xiong, Q.; Feng, B.; Xu, Y.; Zhang, J.; Wang, H. Low-temperature processed SnO2 compact layer for
efficient mesostructure perovskite solar cells. Appl. Surf. Sci. 2017, 391, 677–683. [CrossRef]
31. Correa Baena, J.P.; Steier, L.; Tress, W.; Saliba, M.; Neutzner, S.; Matsui, T.; Giordano, F.; Jacobsson, T.J.;
Kandada, A.R.; Zakeeruddin, S.M.; et al. Highly efficient planar perovskite solar cells through band
alignment engineering. Energy Environ. Sci. 2015, 8, 2928–2934. [CrossRef]
32. Anaraki, E.H.; Kermanpur, A.; Steier, L.; Domanski, K.; Matsui, T.; Tress, W.; Saliba, M.; Abate, A.; Grätzel, M.;
Hagfeldt, A.; et al. Highly efficient and stable planar perovskite solar cells by solution-processed tin oxide.
Energy Environ. Sci. 2016, 9, 3128–3134. [CrossRef]
33. Ke, W.; Fang, G.; Liu, Q.; Xiong, L.; Qin, P.; Tao, H.; Wang, J.; Lei, H.; Li, B.; Wan, J.; et al. Low-temperature
solution-processed tin oxide as an alternative electron transporting layer for efficient perovskite solar cells.
J. Am. Chem. Soc. 2015, 137, 6730–6733. [CrossRef] [PubMed]
34. Yang, G.; Wang, C.; Lei, H.; Zheng, X.; Qin, P.; Xiong, L.; Zhao, X.; Yan, Y.; Fang, G. Interface engineering in
planar perovskite solar cells: Energy level alignment, perovskite morphology control and high performance
achievement. J. Am. Chem. Soc. 2017, 5, 1658–1666. [CrossRef]
35. Park, M.; Kim, J.Y.; Son, H.J.; Lee, C.H.; Jang, S.S.; Ko, M.J. Low-temperature solution-processed Li-doped
SnO2 as an effective electron transporting layer for high-performance flexible and wearable perovskite solar
cells. Nano Energy 2016, 26, 208–215. [CrossRef]
36. Dong, Q.; Wang, M.; Zhang, Q.; Chen, F.; Zhang, S.; Bian, J.; Ma, T.; Wang, L.; Shi, Y. Discontinuous
SnO2 derived blended-interfacial-layer in mesoscopic perovskite solar cells: Minimizing electron transfer
resistance and improving stability. Nano Energy 2017, 38, 358–367. [CrossRef]
37. Zuo, L.; Chen, Q.; De, M.N.; Hsieh, Y.T.; Chen, H.; Sun, P.; Chang, S.Y.; Zhao, H.; Dong, S.; Yang, Y. Tailoring
the Interfacial Chemical Interaction for High-Efficiency Perovskite Solar Cells. Nano Lett. 2017, 17, 269–275.
[CrossRef] [PubMed]
38. Song, J.; Zheng, E.; Wang, X.F.; Tian, W.; Miyasaka, T. Low-temperature-processed ZnO–SnO2 nanocomposite
for efficient planar perovskite solar cells. Sol. Energy Mater. Sol. Cells 2016, 144, 623–630. [CrossRef]
39. Yu, Y.; Wang, C.; Grice, C.R.; Shrestha, N.; Chen, J.; Zhao, D.; Liao, W.; Cimaroli, A.J.; Roland, P.J.;
Ellingson, R.J.; et al. Improving the Performance of Formamidinium and Cesium Lead Triiodide Perovskite
Solar Cells using Lead Thiocyanate Additives. ChemSusChem 2016, 9, 3288–3297. [CrossRef] [PubMed]
40. Bube, R.H. Trap Density Determination by Space-Charge-Limited Currents. J. Appl. Phys. 1962, 33, 1733–1737.
[CrossRef]
41. Tan, H.; Jain, A.; Voznyy, O.; Lan, X.; de Arquer, F.P.G.; Fan, J.Z.; Quintero-Bermudez, R.; Yuan, M.; Zhang, B.;
Zhao, Y.; et al. Efficient and stable solution-processed planar perovskite solar cells via contact passivation.
Science 2017, 355, 722–726. [CrossRef] [PubMed]

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