Applied Materials Today 7 (2017) 112–119

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Applied Materials Today

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TiO2 colloid-based compact layers for hybrid lead halide perovskite solar cells
Sateesh Prathapani a,∗ , Venumadhav More b , Siva Bohm a,c , Parag Bhargava a , Aswani Yella a ,
Sudhanshu Mallick a,∗
a
Department of Metallurgical Engineering & Materials Science, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
b
Centre for Research in Nanotechnology & Science, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
c
Tata Steel R&D, Swinden Technology Center, Moorgate, Rotherham, South Yorkshire S60 3AR, UK

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

Article history: In this report, we present a simple method of TiO2 colloidal preparation and its application to form
Received 1 October 2016 compact conformal TiO2 (c-TiO2 ) layers on transparent conducting substrates. The synthesized colloid
Received in revised form 15 January 2017 has ∼5 nm particle size distribution and is stable over a period exceeding one year. The blocking nature
Accepted 27 January 2017
of c-TiO2 is evaluated by the method of cyclic voltammetry using Spiro-OMeTAD as the redox probe.
This method of c-TiO2 preparation is successfully employed in the fabrication of hybrid perovskite solar
Keywords:
cells. The critical requirement of c-TiO2 colloid-based compact layer as hole-blocking material is justified
TiO2 colloids
with the realization of photo-conversion efficiencies of 8.08% for small active areas of 0.07 cm2 and 7.52%
TiO2 nanoparticles
Titania nanoparticles
with relatively large active areas of 0.23 cm2 in one-step method. In two-step sequential deposition
TiO2 compact layer for perovskite solar cells method, a photo-conversion efficiency of 4.61% is achieved over relatively large active area of 0.64 cm2 .
Our observations suggest that c-TiO2 formation by TiO2 colloid can be an alternative potential route to
approach for perovskite solar cell fabrication. All device processing is carried out in ambient air of relative
humidity 40 ± 5% at room temperature.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Organic–inorganic metal halide perovskite materials are the
new class of hybrid semiconductors with the general formula ABX3 ,
where A and B are organic and inorganic cations and X (Cl, Br and I) is
the halide anion, respectively. The exceptional physical properties
of hybrid perovskite materials like a tunable band gap [1,2], high
absorption coefficient [3], and long-range charge transport with
high mobilities [4] have brought about a surge of interest in the
optoelectronic device community to seek hybrid perovskite mate-
rials as potential candidates for solar cell fabrication [5–7]. The
semiconductor research community has put considerable effort
in aspects of compositional tailoring and device engineering, and
hence have improved the photo-conversion efficiencies of 3.81%
from the first report to as high as 19.3% and 22.1% [5,8,9].
A typical hybrid perovskite solar cell (PSC) device consists of a
total of the following six layers: (i) FTO (fluorine-doped tin oxide)
as transparent electrode, (ii) c-TiO2 as electron transport material
(ETM), which can additionally block the hole from reaching FTO,
(iii) mesoporous TiO2 (mp-TiO2 ) to infiltrate light harvester and to
∗ Corresponding authors.
E-mail addresses: sateesh.prathapani@gmail.com (S. Prathapani),
mallick@iitb.ac.in (S. Mallick).
extract electrons from it, (iv) hybrid perovskite as light harvester,
(v) hole transport material (HTM) to extract holes from perov-
skite and (vi) metal Au as back electrode [7,10,11]. In literature,
perovskite processing is predominantly reported by two methods
of depositions, i.e. one-step deposition and two-step sequential
deposition [7,10–12]. In one-step deposition method, a perovskite
solution in the solvent dimethylformamide (DMF) is formed by
mixing the precursors lead chloride (PbCl2 ) and methylammonium
iodide (CH3 NH3 I) in 1:3 molar ratio, respectively. As-prepared
solution is infiltrated into mp-TiO2 substrates and subsequently
subjected to an annealing process (at 100 ◦ C for 40 min) to form
perovskite thin film. In two-step sequential deposition method, 1 M
lead iodide (PbI2 ) solution in DMF is made and coated on to the mp-
TiO2 substrates. On annealing for 20 min at 100 ◦ C, solid PbI2 films
are formed. Subsequently, these PbI2 films on mp-TiO2 are dipped
in MAI solution (8 mg/ml in 2-propanol) to form perovskite layer at
room temperature. From the literature and with our experimental
observations, we found that it is a challenging task to form a contin-
uous pinhole-free perovskite film on mp-TiO2 [13,14]. Moreover, if
the processing is carried out in ambient air, the moisture in the air
can be the additional factor that can alter the crystallization kinet-
ics of perovskite materials and thus its morphology [13]. One-step
deposition method leaves island kind of discontinued perov-
skite grains, whereas two-step deposition method gives uniform
grains with less pinholes. For the potential development of PSC

http://dx.doi.org/10.1016/j.apmt.2017.01.009
2352-9407/© 2017 Elsevier Ltd. All rights reserved.
 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119
technology, simplification of processing conditions is needed.
Therefore, we have processed our PSC devices in the ambient air,
which may lead to non-uniform perovskite films.
When the perovskite films contain pinholes, the problem arises
that HTM can leak through these pinholes and reach c-TiO2 via
mp-TiO2 . If the c-TiO2 is not conformal on FTO, HTM touches with
it creating shunt paths in device causing recombinations. There-
fore, it is critical to have conformal c-TiO2 on FTO. To deal with
non-uniformly grown perovskite films and to realize the possi-
ble PSC working devices, we have synthesized TiO2 -based colloidal
nanoparticles (NP) for the compact layer (c-TiO2 ) preparation and
fabricated the PSCs.
In literature, the use of TiO2 compact layer for dye-sensitized
and perovskite-sensitized solar cells has been emphasized as effec-
tive hole-blocking material [10,15]. Several methods have been
reported to prepare c-TiO2 , but each of them has its own limitations.
Recently, Kavan et al. evaluated the blocking nature of c-TiO2 grown
by different methods like electrochemical, thermal oxidation, spray
pyrolysis and atomic layer deposition [16,17]. Other solution-based
methods include chemical bath deposition by using TiCl4 and direct
deposition of titanium (IV) isopropoxide (TTIP) solution in acetic
acid. These solution-based methods are also not viable, as TiCl4
vigorously reacts with moisture (while handling in ambient air)
or water and releases toxic hydrochloric acid gas [18]. TTIP-based
solutions form agglomerates on substrate during coating process on
reaction with moisture in air. Hence, an alternative simple solution
route is needed.
Here we report one-step direct synthesis of colloidal TiO2
nanoparticles with some modification to the earlier reported
method [19]. The current route of colloidal formation is water-
based environmental friendly method, which is non-hazardous,
amenable for large-scale production, inexpensive and can be han-
dled in ambient condition without creating any agglomerates.
These TiO2 colloids are stable for a period exceeding a year without
forming any agglomerates or precipitates and are suitable for dip-,
spin- and spray-coating techniques to form thin and compact TiO2
films. By using these compact layers, perovskite solar cells have
been fabricated in ambient conditions with various active areas
and realized considerable photo-conversion efficiencies (PCE) with
better stability.
2. Experimental details
2.1. Materials
Chemicals titanium (IV) isopropoxide (TTIP) (97%), lead chlo-
ride (PbCl2 , 98%), lead iodide (PbI2 , 99%), hydroiodic acid
(HI, 57 wt% in water), chlorobenzene (anhydrous 99.8%), N,N-
dimethylformamide (DMF, anhydrous 99.8%), and acetonitrile
(anhydrous 99.8%) were bought from Sigma–Aldrich and used
as received. The other chemicals like HNO3 (65% assay) was
bought from Merck Millipore, Methylamine (40% in methanol)
from TCI chemicals and bis(trifluoromethane)sulfonamide lithium
(LiTFSI, 98%) salt from Alfa Aesar. TiO2 paste 18NR-T grade,
fluorine-doped tin oxide on glass (FTO) (sheet resistance
7 /sq) and 2,2 ,7,7 -tetrakis(N,N-di-p-methoxyphenyl-amine)-
9,9 -spirobifluorene (spiro-MeOTAD) were procured from Dyesol.
2.2. Synthesis of TiO2 colloids
To synthesize TiO2 colloids, first, a stock solution of 0.1 M HNO3
in distilled water was prepared. From the stock solution, 72 g
of 0.1 M HNO3 was taken in a 150 ml round bottom flask and
immersed in an oil bath. 12 g of TTIP was added drop by drop
into the stock solution while stirring at room temperature. After
113
the TTIP addition, the temperature of the oil bath was raised to
80 ◦ C and kept so for 12 h. In the initial stage with the addition
of TTIP, the solution turned milky white in color due to hydroly-
sis, and after few hours with constant stirring, the entire solution
converted into transparent white with complete formation of TiO2
colloid. After this step, the solution was cooled down to room tem-
perature and stored. A very slow addition of TTIP into the HNO3
stock solution is critical to control the particle size of TiO2 colloid.
As-formed colloids are stable over a period exceeding a year at room
temperature.
2.3. Synthesis of precursors for perovskite materials
The precursor material methylammonium iodide (CH3 NH3 I –
MAI) was synthesized by reacting equimolar ratio of methyl amine
and Hydroiodic acid in a round bottom flask at temperature 5–10 ◦ C
in an ice bath. The reacted solution was heated in open air at
50 ◦ C for 30 min, which yielded a white color solid product. This
product was washed with anhydrous diethyl ether three times
and dissolved in dry ethanol. By using rotary evaporator main-
tained at 50 ◦ C, ethanol was taken out which lead to the formation
of white crystals. These white crystals are of MAI as confirmed
from XRD study (Supplementary Fig. S1). This obtained product
MAI was kept in a vacuum oven for 24 h and finally stored in
nitrogen-filled glove box [5–7]. For one-step deposition method,
the perovskite precursor solution was prepared by mixing CH3 NH3 I
and PbCl2 in 3:1 molar ratio in DMF to prepare 40 wt% of perovskite
(CH3 NH3 PbI3−x Clx ) and stirred for 10 h at a constant temperature
of 70 ◦ C and obtained a transparent yellow solution [5–8]. For two-
step sequential deposition method, 1 M PbI2 solution in DMF was
prepared to coat on to the mesoporous TiO2 layers. The concentra-
tion of MAI in 2-propanol was 8 mg/ml.
2.4. Perovskite solar cells fabrication
The fabrication procedure for PSC devices involves several steps.
First, FTO substrates were cleaned with soap solution, deionized
water and ethanol by keeping in ultrasonic water bath for 15 min
at each step. Then these FTO substrates were heated to 450 ◦ C
for 30 min to remove the residual organics. The cleaned FTO sub-
strates were coated with colloidal TiO2 by spin-coating method and
heated to 500 ◦ C for 30 min to form c-TiO2 . For mp-TiO2 forma-
tion, slurry was prepared by using Dyesol 18 NR-T paste mixed
in ethanol in 1:4 weight ratios (TiO2 to ethanol). As-formed TiO2
slurry is spin coated on top of c-TiO2 and sintered at 500 ◦ C for
20 min. For one-step deposition, at room temperature, the above-
prepared FTO/c-TiO2 /mp-TiO2 substrates were spin coated with
previously made perovskite solution in ambient air at 40 ± 5% RH
and annealed at 100 ◦ C in nitrogen environment for perovskite
formation. The spin-coating parameters for all above processes
used were 5000 rpm for 30 s. For two-step sequential deposition
method, first 1 M lead iodide solution was coated on to FTO/c-
TiO2 /mp-TiO2 substrates and heated to 100 ◦ C for 20 min and
cooled down to room temperature. Then, these substrates were
dipped in MAI solution at room temperature for 1 min to com-
pletely convert PbI2 into perovskite (CH3 NH3 PbI3 ) and annealed
for 20 s at 70 ◦ C in ambient conditions. After annealing of perovskite
materials in both the methods, HTM was coated (in ambient condi-
tions) with the same spinning parameters as that of other material.
The formulation for HTM used was 80 mg/ml of Spiro-MeOTAD in
chlorobenzene with the additives 17.5 ␮l of LiTFSI (from the stock
solution of LiTFSI 520 mg/ml in acetonitrile) and 29.5 ␮l of tert-
butyl pyridine [15]. Finally, metal Au was evaporated on to HTM
to make the back contact; then, I–V measurements were carried
out.
114 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119
Fig. 1. TEM images for TiO2 colloid: (a) high-resolution image, which confirms ∼5 nm size, (b) the uniform size distribution of colloid NP over the TEM grid, (c) XRD
spectrogram showing TiO2 phase information as anatase, and (d) bottle containing synthesized TiO2 colloid.
2.5. Characterization
TiO2 colloids crystalline phase information was confirmed by
X-ray diffraction with X-ray diffractometer model PANalytical –
MRDTM . TiO2 particle size distribution and its conformal thin
film formation on FTO were studied by using TEM- model JEOL-
JEM 2100F and FEG-SEM model JEOL JSM-7600F, respectively.
Absorption/transmission measurements were carried out by using
UV–Visible–NIR spectrophotometer model Jasco V-650; for trans-
mission measurements, integrating sphere was employed with
BaSO4 as standard reference to account for reflection losses. The
current density–voltage characteristics for the fabricated PSCs were
obtained by using standard solar simulator with 150 W Xenon
arc-lamp model NEW PORT-92251A-1000 attached with keithley-
2420 source meter under one sun (AM 1.5, 100 mW/cm2 ). Cyclic
voltammetry measurements were carried out by using potentio-
stat/galvanostat model PGSTAT 302 N Metrohm Autolab attached
with NOVA software.
3. Results and discussion
3.1. TiO2 colloid
Fig. 1(a) shows the high-resolution transmission electron
microscopy image confirming the ∼5 nm size of as-prepared
TiO2 nanoparticles; their uniform size distribution is shown by
low-magnification TEM image in Fig. 1(b). For crystallography
information XRD studies were carried out for the colloids by drop
casting on Plain glass and the results are shown in Fig. 1(c),
which confirm that these colloids are single crystals of anatase
phase having the diffraction peaks matching with the standard
crystallographic data, with JCPDS card no. 21-1272. The observed
peaks in the XRD pattern are very broad indicating qualitatively
the presence of very small nanoparticles. By considering high-
est intensity peak (101), the crystallite size is calculated by using
Debye–Scherrer’s equation (D = 0.9/ˇ cos ; D – particle size,  –
wavelength of X-rays, ˇ – full width at half maxima of correspond-
ing peak and  – Bragg angle), and it is found that the crystallite
size is of ∼5 nm, which is in agreement with the observed particle
size in TEM results. A photograph of the prepared colloids is shown
in Fig. 1(d).
Size-dependent quantization effects for extremely small TiO2
particles were reported earlier [20–22]. To test the possible quan-
tum confinement effects for these colloids, absorbance studies were
carried out. Fig. 2 shows the absorbance response of the colloids
with an absorption edge at 340 nm corresponding to band gap of
3.64 eV. However, from the literature it is understood that TiO2 in
anatase phase has an indirect band gap of 3.2 eV [23–25]. To con-
firm the actual band gap of these colloids, Tauc plots were made
for direct [(Ah)2 vs. h; A – absorbance, h – plank’s constant and
 – frequency of light] and indirect [(Ah)1/2 vs. h] allowed transi-
tions as shown in Fig. 2 inset. The abscissa of the intercepts for these
two curves on energy (h) axis gives the band gaps for direct and
indirect transitions, respectively. On observing these band gap esti-
mations with the help of these allowed transition plots (as shown in
 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119 115

3.2. TiO2 compact layer from colloid

For solar cell applications, transmittance of substrates is con-

sidered to be a paramount factor to pass light through them and to
check that preliminarily sintered TiO2 compact films of ∼145 nm
and 40 nm average thicknesses were made by dip- and spin-coating
of TiO2 colloids on FTO respectively (Fig. 3(a) and (b), respectively).
In general, the surface roughness of FTO is around 20 nm (Fig. S2);
the prepared TiO2 colloids with ∼5 nm size can effectively fill the
hillocks on FTO and form a continuous dense compact layer with
full coverage as shown in SEM top view images in Fig. 3(c) and (d).
Apparently, it is evident from Fig. 3(c) and (d) that there are no vis-
ible cracks or pinholes in c-TiO2 films. These FTO/c-TiO2 substrates
were subjected to transmittance test over 300–800 nm of incident
light, which is from far ultraviolet to near infrared region as shown
in Fig. 4. In this regime, FTO has a transmittance of 80–85% and for
spin- and dip-coated FTO/c-TiO2 , it is of about 75–80%, which is
considerable to use for solar cell fabrication.

Fig. 2. Absorbance of TiO2 colloids (inset – Tauc plots).

3.3. Cyclic voltammetry

Kavan et al. applied the cyclic voltammetry (CV) method as

Fig. 2 inset), it is clear that in ‘direct transition curve,’ the intercept
is at 3.64 eV that corresponds to direct inter band gap, and for ‘indi-
rect transition curve,’ the intercept is at 3.23 eV that corresponds to
‘indirect band gap’. These observed energy band gap results are in
good agreement with the earlier reports [23,24]. Since the lowest
value is considered to be the band gap, it can be concluded that
for the ∼5 nm particle size TiO2 colloids, the band gap is of indirect
type with 3.23 eV and no quantum confinement effects have been
seen. Therefore, the colloids are considered to be nanoparticles of
∼ 5 nm sizes and are not the quantum dots.
a potential technique to evaluate the blocking nature of c-TiO2
[16,17]. On adopting this method the blocking nature of spin-
coated c-TiO2 films on FTO was evaluated and compared with bare
FTO. As Spiro-OMeTAD is the HTM used in perovskite solar cells,
a redox probe based on the same can better justify the blocking
nature of c-TiO2 . Therefore, the composition of electrolyte chosen
was 1 mM Spiro-MeOTAD in Dichloromethane with the addition of
0.3 M Tetrabutylammonium hexafluorophosphate [16,17]. Three
electrode system was used for CV, where Ag/AgCl was reference, Pt
was auxiliary and c-TiO2 or FTO was working electrode. Fig. 5 shows

Fig. 3. FEG-SEM images: (a) cross-section view showing sintered dense c-TiO2 film on FTO formed by dip-coating with minimum thickness 114 nm and a maximum of
174 nm (average of ∼145 nm), (b) cross-section view of sintered c-TiO2 on FTO formed by spin-coating method with 40 nm thickness, (c) high-resolution top-view showing
full coverage of FTO surface hillocks by c-TiO2 , and (d) large area top-view image showing absence of visible cracks in c-TiO2 .
116 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119
Fig. 4. Transmittance of c-TiO2 formed on FTO by dip- and spin-coating method in
comparison with FTO.
Fig. 5. Cyclic voltammograms corresponding to bare FTO and 40-nm thick C-
TiO2 on FTO (FTO/c-TiO2 ). The electrolyte composition: 1 mM Spiro-OMeTAD
in Dichloromethane + 0.3 M Tetrabutylammonium hexafluorophosphate. Scan rate
50 mV/s.
the cyclic voltammograms for c-TiO2 and bare FTO. The cracks or
pinholes on sintered c-TiO2 can be monitored by observing the
occurrence of anodic current due to oxidation of Spiro-OMeTAD
at exposed FTO regions. From these voltammograms, it is clear
that the observed anodic current density is much smaller for FTO/
c-TiO2 on compared with bare FTO proving the blocking nature of
c-TiO2 .
3.4. PSCs fabrication and their performance evaluation
The critical step in the device fabrication is the formation of
crystalline perovskite film with good continuity on to the mp-TiO2 .
Therefore, before the device fabrication, the perovskite film for-
mation studies were carried out in view of perovskite infiltration
and surface coverage. Fig. 6(a) shows the cross-section view of
the infiltrated perovskite onto the mp-TiO2 (by one-step method),
which is about 440 nm. From the literature it is understood that
the perovskite materials with the thickness of 440 nm can have
good optical density [26]. In accordance with the earlier literature,
the microstructure of as-formed one-step film was non-uniform
with perovskite islands on mp-TiO2 as shown in Fig. 6(b) [13,27,28].
But, with the two-step sequential deposited method, we obtained
comparatively better uniform films as shown in Fig. 6(c). From the
literature we note that the factors affecting the uniformity of the
perovskite films are wettability and thus nucleation and growth
[13], the presence of humidity [13,29], type of precursors taken
and their concentration [14,30,31], the annealing temperatures and
time of annealing [27,30–32], formation of intermediate products
and their volatilization [30,33], etc. In one-step method, during fast-
spinning process, a fraction of perovskite phase was formed even at
room temperature along with some amount of residual PbI2 , which
is confirmed from XRD studies as shown in Fig. 6(d), and labeled as
MALI-BA (before annealing). After annealing process at 100 ◦ C for
40 min, a complete perovskite phase was achieved; this is indicated
as MALI-AA in Fig. 6(d). The perovskite phase confirmation for the
films made by sequential deposition method is shown in Fig. 6(d)
with the label ‘Two-step MALI’.
The entire device architecture with its energy band diagram is
shown in Fig. 7(a) and (b), respectively. Since, the estimated energy
gap for colloidal TiO2 NP is of 3.2 eV, which is in accordance with
the energy gap for bulk TiO2 [23–25], the same band gap is consid-
ered for both c-TiO2 and mp-TiO2 for Fig. 7(b). In a typical working
device, when light shines, electron–hole pairs are generated (elec-
tron being in conduction band and holes being in valence band of
perovskite) in perovskite materials. Instantly, the electrons move
from perovskite conduction band to ETM, i.e. TiO2 conduction band,
and reach FTO. In the same way, holes move from valence band of
perovskite to the highest occupied molecular orbit (HOMO level) of
HTM, i.e. to Spiro-MeOTAD, and then reach back electrode Au com-
pleting the circuit. The entire mechanism is depicted in Fig. 7(b); the
energy-level values for the various materials are considered from
the literature [7,34].
Fig. 8 shows the current density vs. voltage (J–V) characteristics
for the fabricated best PSC devices processed in ambient condi-
tions. The highest PCE () achieved through one-step process was
8.08% for an active area of 0.07 cm2 and the devices with an active
area of 0.23 cm2 achieved a best efficiency of 7.52% as shown in
Fig. 8(a) and (b), respectively. For 0.64 cm2 , the observed efficiency
was very low. A batch of three cells for each active area has been
prepared and their mean PCE values are tabulated along with the
best cell parameters in Table 1. In two-step method, the perov-
skite morphology and thickness are decided by the PbI2 layer. The
thickness of the PbI2 layer can be varied more efficiently with the
deposition parameters, and later it can be converted into perov-
skite by dipping in MAI solution. PSCs were made with 600-nm
thick perovskite films (Fig. S3) and tested for their intrinsic sta-
bility against ambient moisture by storing them in a shelf in dark
without any encapsulation. These thick PSCs show stable perfor-
mance with only 3% degradation up to 500 h as shown in Fig. 8(c).
Complete test details with respect to aging time are presented in
Table 2. It is to be noted that the PSCs fabricated by both the meth-
ods have shown considerable hysteresis (Fig. S4). Fig. 8(d) shows
the photographs of 0.23 and 0.64 cm2 PSCs.
The reason for observed low efficiencies can be understood in
the following way. The ability of charge collection, recombina-
tions and their effect on quasi-Fermi-level movement in ETL are
considered to be the major reasons for the VOC loss [30,35,36].
In one-step method, the poorly covered island kind of perovskite
has large areas of exposed TiO2 in contact with HTM causing the
recombination of holes in the perovskite with the electrons in TiO2 ,
thus reducing the electron charge density of TiO2 . This reduction
in charge density in TiO2 can cause the lowering of quasi-Fermi
energy-level, thus leading to the reduction in the measured VOC .
Since in two-step deposition method the perovskite coverage is
comparatively better than the one-step, comparatively better VOC
is achieved. In one-step method, due to the considerable thickness
(400 nm) of the perovskite active layer, it can have large optical
density leading to the higher JSC values (for small areas), whereas
in two-step method, due to large thickness (600 nm), some carriers
 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119 117

Fig. 6. (a and b) FEG-SEM images showing cross-section and surface morphology of infiltrated perovskite into TiO2 at RH 40 ± 5%, respectively via one-step method, (c)
FEG-SEM image showing top view of perovskite film formed by two-step method, and (d) XRD of perovskite films in one and two-step process.

Fig. 7. (a and b) Architecture and energy-level diagram for the various layers for PSC device, respectively.

Table 1
CH3 NH3 PbI3−x Clx PSCs performance parameters form J–V measurements by one-step method.

Cell area (cm2 ) Category (one-step) JSC (mA/cm2 ) VOC (V) FF  (%)

0.07 Best (mean) 18.52 (15.77 ± 2.47) 0.713 (0.703 ± 0.01) 0.61 (0.59 ± 0.05) 8.08 (6.68 ± 1.51)
0.23 Best (mean) 18.07 (15.30 ± 2.49) 0.743 (0.734 ± 0.01) 0.56 (0.55 ± 0.03) 7.52 (6.31 ± 1.33)
0.64 Best (mean) 4.40 (4.19 ± 0.66) 0.589 (0.612 ± 0.04) 0.68 (0.54 ± 0.09) 1.76 (1.38 ± 0.27)

Table 2
CH3 NH3 PbI3 PSC performance parameters prepared by two-step sequential deposition method and performance variation with the aging time (cell active area is 0.64 cm2 ).

Time (h) JSC (mA/cm2 ) VOC (V) FF  (%) Degradation (%)

0 12.4 0.82 0.45 4.61 –

500 10.46 0.85 0.5 4.47 3.00
1200 7.36 0.8 0.47 2.75 40.34
118 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119

Fig. 8. J–V characteristic curves for the best PSC devices (a) 0.07 cm2 active area with PCE of 8.08% (one-step), (b) 0.23 cm2 active area with PCE of 7.52% (one step), (c)
0.64 cm2 active area with PCE of 4.61% and its performance degradation with aging time (0 h represents immediate measurement after the PSC fabrication within an hour),
and (d) figure showing pictures of fabricated large active area cells by one- and two-step methods.

may be lost in recombination leading to comparatively low JSC . As Acknowledgements

observed from the FEG-SEM images, the grain size of the perov-
skite in sequential deposition method is smaller; therefore, there
might be grain boundary contributions for recombinations, which
may further affect VOC and JSC [37,38]. Performance parameters for
a series of devices fabricated under ambient conditions at room
temperature are given in Table S1.
4. Conclusion
In summary, TiO2 colloids were synthesized and used to form
c-TiO2 on FTO. The blocking nature of c-TiO2 was confirmed by
the method of cyclic voltammetry using Spiro-MeOTAD as redox
probe. Non-uniform perovskite film morphologies were observed
with ambient processing. The method of TiO2 colloid-based com-
pact layer formation was emphasized as effective hole-blocking
layers for PSCs processed under ambient conditions with observed
photo-conversion efficiency of 8.08% for small active area 0.07 cm2
and 7.52% for relatively large active area of 0.23 cm2 via one-
step method. In two-step sequential method, comparatively better
perovskite coverage was observed, and therefore PSCs with com-
paratively large active areas of 0.64 cm2 show PCE of 4.61% with
considerable stability in ambient air.
The authors sincerely acknowledge Devices & Interfaces Lab-
oratory, IIT Bombay for metallization and device measurement
facilities, and Dr. Chris Moore – Dyesol UK Limited for provid-
ing Spiro-MeOTAD and TiO2 Materials. The financial and analytical
facilities provided by SERIIUS (Solar Energy Research Institute for
India and the United States), NCPRE and SAIF at IIT Bombay and
central funding agencies MNRE and DST are greatly acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.apmt.2017.01.009.
References
[1] B. Suarez, V. Gonzalez-Pedro, T.S. Ripolles, R.S. Sanchez, L. Otero, I. Mora-Sero,
Recombination study of combined halides (Cl, Br, I) perovskite solar cells, J.
Phys. Chem. Lett. 5 (2014) 1628–1635.
[2] T.B. Song, Q. Chen, H. Zhou, C. Jiang, H.-H. Wang, Y. (Michael) Yang, Y. Liu, J.
You, Y. Yang, Perovskite solar cells: film formation and properties, J. Mater.
Chem. A 3 (2015) 9032–9050.
[3] G. Xing, N. Mathews, S. Sun, S.S. Lim, Y.M. Lam, S. Mhaisalkar, T.C. Sum,
Long-range balanced electron- and hole-transport lengths in
organic–inorganic CH3 NH3 PbI3 , Science 342 (2013) 344–347.
 S. Prathapani et al. / Applied Materials Today 7 (2017) 112–119
[4] S.D. Stranks, G.E. Eperon, G. Grancini, C. Menelaou, M.J.P. Alcocer, T. Leijtens,
L.M. Herz, A. Petrozza, H.J. Snaith, Electron–hole diffusion lengths exceeding
1 micrometer in an organometal trihalide perovskite absorber, Science 342
(2013) 341–344.
[5] A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, Organometal halide perovskites
as visible-light sensitizers for photovoltaic cells, J. Am. Chem. Soc. 131 (2011)
6050–6051.
[6] J.H. Im, C.R. Lee, J.W. Lee, S.W. Park, N.G. Park, 6.5% efficient perovskite
quantum-dot-sensitized solar cell, Nanoscale 3 (2011) 4088–4093.
[7] H.S. Kim, C.R. Lee, J.H. Im, K.B. Lee, T. Moehl, A. Marchioro, S.J. Moon, R.
Humphry-Baker, J.H. Yum, J.E. Moser, M. Grätzel, N.G. Park, Lead iodide
perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell
with efficiency exceeding 9%, Sci. Rep. 2 (2012) 591, 1–7.
[8] H. Zhou, Q. Chen, G. Li, S. Luo, T.B. Song, H.S. Duan, Z. Hong, J. You, Y. Liu, Y.
Yang, Interface engineering of highly efficient perovskite solar cells, Science
345 (2014) 542–546.
[9] http://www.nrel.gov/ncpv/images/efficiency chart.jpg (accessed on 03.06.16).
[10] A. Yella, L.P. Heiniger, P. Gao, M.K. Nazeeruddin, M. Grätzel, Nanocrystalline
rutile electron extraction layer enables low-temperature solution processed
perovskite photovoltaics with 13.7% efficiency, Nano Lett. 14 (2014) 2591.
[11] J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M.K. Nazeeruddi,
M. Grätzel, Sequential deposition as a route to high-performance
perovskite-sensitized solar cells, Nature 499 (2013) 316–319.
[12] M.M. Lee, J. Teuscher, T. Miyasaka, T.N. Murakami, H.J. Snaith, Efficient hybrid
solar cells based on meso-superstructured organometal halide perovskites,
Science 338 (2012) 643–647.
[13] H. Gao, C. Bao, F. Li, T. Yu, J. Yang, W. Zhu, X. Zhou, G. Fu, Z. Zou, Nucleation
and crystal growth of organic–inorganic lead halide perovskites under
different relative humidity, ACS Appl. Mater. Interfaces 7 (2015) 9110–9117.
[14] B. Philippe, B.-W. Park, R. Lindblad, J. Oscarsson, S. Ahmadi, E.M.J. Johansson,
H. Rensmo, Chemical and electronic structure characterization of lead halide
perovskites and stability behavior under different exposures – a
photoelectron spectroscopy investigation, Chem. Mater. 27 (2015)
1720–1731.
[15] A.K. Chandiran, A. Yella, M. Stefik, L.-P. Heiniger, P. Comte, M.K. Nazeeruddin,
M. Grätzel, Low-temperature crystalline titanium dioxide by atomic layer
deposition for dye-sensitized solar cells, ACS Appl. Mater. Interfaces 5 (2013)
3487.
[16] L. Kavan, M. Zukalova, O. Vik, D. Havlicek, Sol–gel titanium dioxide blocking
layers for dye-sensitized solar cells: electrochemical characterization, Chem.
Phys. Chem. 15 (2014) 1056–1061.
[17] L. Kavan, N. Tétreault, T. Moehl, M. Grätzel, Electrochemical characterization
of TiO2 blocking layers for dye-sensitized solar cells, J. Phys. Chem. C 118
(2014) 16408–16418.
[18] P.K. Roy, A. Bhatt, C. Rajagopal, Quantitative risk assessment for accidental
release of titanium tetrachloride in a titanium sponge production plant, J.
Hazard. Mater. A102 (2003) 167–186.
[19] W. Choi, A. Termin, M.R. Hoffmann, The role of metal ion dopants in
quantum-sized TiO2 : correlation between photoreactivity and charge carrier
recombination dynamics, J. Phys. Chem. 98 (1994) 13669–13679.
[20] M. Anpo, T. Shima, S. Kodama, Y. Kubokawa, Photocatalytic hydrogenation of
CH3 CCH with H2 O on small-particle TiO2 : size quantization effects and
reaction intermediates, J. Phys. Chem. 91 (1987) 4310–4317.
[21] C. Kormann, D.W. Bahnemann, M.R. Hoffmann, Preparation and
characterization of quantum-size titanium dioxide, J. Phys. Chem. 92 (1988)
5201–5205.
119
[22] L. Kavan, T. Stoto, M. Grätzel, D. Fitzmaurice, V. Shklover, Quantum size
effects in nanocrystalline semiconducting TiO2 layers prepared by anodic
oxidative hydrolysis of TICl3 , J. Phys. Chem. 97 (1993) 9493–9498.
[23] D.O. Scanlon, C.W. Dunnill, J. Buckeridge, S.A. Shevlin, A.J. Logsdail, S.M.
Woodley, C.R.A. Catlow, M.J. Powell, R.G. Palgrave, I.P. Parkin, G.W. Watson,
T.W. Keal, P. Sherwood, A. Walsh, A.A. Sokol, Band alignment of rutile and
anatase TiO2 , Nat. Mater. 12 (2013) 798–801.
[24] N. Serpone, D. Lawless, R. Khairutdinov, Size effects on the photophysical
properties of colloidal anatase TiO2 particles: size quantization or direct
transitions in this indirect semiconductor? J. Phys. Chem. 99 (1995)
16646–16654.
[25] I. Chung, B. Lee, J. He, R.P.H. Chang, M.G. Kanatzidis, All-solid-state
dye-sensitized solar cells with high efficiency, Nature 485 (2012) 486–489.
[26] T. Leijtens, B. Lauber, G.E. Eperon, S.D. Stranks, H.J. Snaith, The importance of
perovskite pore filling in organometal mixed halide sensitized TiO2 -based
solar cells, J. Phys. Chem. Lett. 5 (2014) 1096–1102.
[27] B. Conings, A. Babayigit, T. Vangerven, J. D’Haen, J. Manca, H.-G. Boyen, The
impact of precursor water content on solution processed organometal halide
perovskite films and solar cells, J. Mater. Chem. A 3 (2015) 19123–19128.
[28] G.E. Eperon, S.N. Habisreutinger, T. Leijtens, B.J. Bruijnaers, J.J. van Franeker,
D.W. deQuilettes, S. Pathak, R.J. Sutton, G. Grancini, D.S. Ginger, R.A.J. Janssen,
A. Petrozza, H.J. Snaith, The importance of moisture in hybrid lead halide
perovskite thin film fabrication, ACS Nano 9 (2015) 9380–9393.
[29] J.A. Christians, P.A. Miranda Herrera, P.V. Kamat, Transformation of the excited
state and photovoltaic efficiency of CH3 NH3 PbI3 perovskite upon controlled
exposure to humidified air, J. Am. Chem. Soc. 137 (2015) 1530–1538.
[30] F.K. Aldibaja, L. Badia, E. Mas-Marza, R.S. Sanchez, E.M. Barea, I. Mora-Sero,
Effect of different lead precursors on perovskite solar cell performance and
stability, J. Mater. Chem. A 3 (2015) 9194–9200.
[31] D. Khatiwada, S. Venkatesan, N. Adhikari, A. Dubey, A.F. Mitul, L. Mohammad,
A. Iefanova, S.B. Darling, Q. Qiao, Efficient perovskite solar cells by
temperature control in single and mixed halide precursor solutions and films,
J. Phys. Chem. C 119 (2015) 25747–25753.
[32] A.T. Mallajosyula, K. Fernando, S. Bhatt, A. Singh, B.W. Alphenaar, J.-C.
Blancon, W. Nie, G. Gupta, A.D. Mohite, Large-area hysteresis-free perovskite
solar cells via temperature controlled doctor blading under ambient
environment, Appl. Mater. Today 3 (2016) 96–102.
[33] B. Wang, K.Y. Wong, X. Xiao, T. Chen, Elucidating the reaction pathways in the
synthesis of organolead trihalide perovskite for high-performance solar cells,
Sci. Rep. 5 (2015) 1–11, 10557.
[34] Y. Song, S. Lv, X. Liu, X. Li, S. Wang, H. Wei, D. Li, Y. Xiao, Q. Meng, Energy level
tuning of TPB-based hole-transporting materials for highly efficient
perovskite solar cells, Chem. Commun. 50 (2014) 15239–15242.
[35] F. Fabregat-Santiago, J. Bisquert, L. Cevey, P. Chen, M. Wang, S.M. Zakeeruddin,
M. Grätzel, Electron transport and recombination in solid-state dye solar cell
with Spiro-OMeTAD as hole conductor, J. Am. Chem. Soc. 131 (2009) 558–562.
[36] H.J. Snaith, Estimating the maximum attainable efficiency in dye-sensitized
solar cells, Adv. Funct. Mater. 20 (2010) 13–19.
[37] R. Long, J. Liu, O.V. Prezhdo, Unravelling the effects of grain boundary and
chemical doping on electron–hole recombination in CH3 NH3 PbI3 perovskite
by time domain atomistic simulation, J. Am. Chem. Soc. 138 (2016)
3884–3890.
[38] N. De Marco, H. Zhou, Q. Chen, P. Sun, Z. Liu, L. Meng, E.-P. Yao, Y. Liu, A.
Schiffer, Y. Yang, Guanidinium: a route to enhanced carrier lifetime and
open-circuit voltage in hybrid perovskite solar cells, Nano Lett. 16 (2016)
1009–1016.