Solar Energy Materials and Solar Cells 185 (2018) 145–152

Contents lists available at ScienceDirect

Solar Energy Materials and Solar Cells

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

Dual-step thermal engineering technique: A new approach for fabrication of T

efficient CH3NH3PbI3-based perovskite solar cell in open air condition
⁎
Sk Abdul Moyez, Subhasis Roy
Department of Chemical Engineering, University of Calcutta, 92 A. P. C. Road, Kolkata 700009, India

A R T I C LE I N FO A B S T R A C T

Keywords: Fabrication of most-promising CH3NH3PbI3 based perovskite solar cell in ambient condition is excessively es-
Perovskite sential to industrialize this revolutionary development. In this research work, an efficient, facile and economical
Solar cell technique has been developed to fabricate CH3NH3PbI3 perovskite solar cell in ambient condition which is
Thermal engineering termed as dual-step thermal engineering technique. In this dual-step thermal engineering technique, the per-
Epitaxial growth
ovskite precursor solution has been spin coated over a mildly hot substrate which was heated at 60 ⁰C for 10 min
and followed by annealing at 80 °C for 30 min immediately after spin coating and compared with the perovskite
film fabricated by conventional annealing in which the film was heated once at 120 °C for 60 min after spin
coating. The comparative study shows that the newly developed dual-step thermal engineering technique is
highly efficient and forms smooth, dense, well-crystallize, almost pinhole free perovskite solar cell at open air
condition and exhibit remarkable enhanced efficiency over conventional annealing. This is because the precursor
solution spontaneously started to develop a perovskite layer over the substrate during spin coating similarly as
epitaxial-growth by utilizing the kinetic energy of the hot substrate and it serves as foundation layer for the high
quality device.

1. Introduction condition [18,21]. Recent literature shows that an attractive, efficient

Emerging CH3NH3PbI3-based perovskite renewable energy har-
vesting technology has snatched attention due to its capability to en-
counter the rapidly growing global energy demand. Due to raw mate-
rials availability, ease manufacturing process, attractive
semiconducting and optoelectronic properties [1–6], long-range ambi-
polar transport characteristics [7], high dielectric constants, low ex-
citon binding energies [8,9], intrinsic ferroelectric polarizations
[10,11] and spin-dependent responses [12,13], the perovskite solar cell
has strengthened the aspect as future energy harvesting technology.
Numerous researches are dedicatedly going on globally to find out a
suitable manufacturing method to commercialize the perovskite pho-
tovoltaic device. As outcomes, dozens of fabrications method has al-
ready been developed like one-step spin-coating technique [14], vapor-
assisted solution procedure [15], two-step spin-coating method [16],
different annealing treatments [17,18], solvent-solvent extraction me-
chanism [19] and sequential deposition method [20]. Majority of re-
search groups have followed different fabrication techniques but, in
most cases, the basic similarities, i.e., uses of nitrogen environment, in
device fabrication is present to fend off air-moisture and simultaneously
very few have reported device formulation techniques at ambient
and effective fabrication procedure is necessary to accelerate the in-
dustrialization of perovskite solar cell and hence the simple hetero-
junction structure and annealing at open air atmosphere are the best
combination to promote bulk production of perovskite photovoltaic
device. But factor like the instability of perovskite material
(CH3NH3PbI3), due to air moisture affects can damage the device
quality. Fabrication of perovskite solar cell with appropriate annealing
or thermal energy treatment could be an effective way to suppress the
obstructing parameter behind perovskite solar cell fabrication at open
air condition. Few attractive planar heterojunction perovskite solar cell
and its rebuilding improvement mechanism has already been reported
[22–24]. Highly hygroscopic methylammonium cation [(CH3NH2)+]
can enhances the device efficiency by enlarging CH3NH3PbI3 crystal
besides its detrimental and degradation tendency to CH3NH3PbI3 per-
ovskite solar cell by absorbing moisture during air-annealing [22]. So,
the fabrication of CH3NH3PbI3 perovskite solar cells in presence of air
could be beneficial besides its degradation hindrance. Therefore, an
effective and efficient fabrication technique is urgently essential to
fabricate the CH3NH3PbI3 perovskite solar cell in open atmosphere
which can control the performance, film's morphology, proper phase
formation. Besides the pure perovskite materials, the application of the

⁎
Corresponding author.
E-mail addresses: subhasis1093@gmail.com, srchemengg@caluniv.ac.in (S. Roy).

https://doi.org/10.1016/j.solmat.2018.05.027
Received 10 March 2018; Received in revised form 1 May 2018; Accepted 11 May 2018
0927-0248/ © 2018 Elsevier B.V. All rights reserved.
S.A. Moyez, S. Roy Solar Energy Materials and Solar Cells 185 (2018) 145–152

2.2. Device fabrication

Fabrication of a complete CH3NH3PbI3 based solar cell device in-

volves combination of several steps together. Concentrate HCl (≥ 98%
pure, Merck Specialities Pvt. Ltd.) and Zn powder (≥ 93% pure, Merck
Specialities Pvt. Ltd.) were used to etched fluorine doped tin oxide
(FTO) glasses (Pilkington, 7 Ω per sq) followed by cleaning with ultra-
sonication using normal water, deionized water, detergent (2%
Hellmanex) in water, acetone (99.5% pure, Sigma Aldrich) and ethanol
(99.5% pure, Merck Specialities Pvt. Ltd.) for 10 min each. The pat-
terned FTO glasses were dried in oven drier for 30 min. Titanium iso-
propoxide (TTIP) (98% purity, Sigma Aldrich) was diluted in ethanol
and spun up at 3000 rpm for 30 s to deposit a thin, compact, trans-
parent, electron transporting layer (ETL) of TiO2 on FTO glasses. This
Fig. 1. Epitaxial growth of CH3NH3PbI3 perovskite thin layer over hot substrate TiO2 layer was sintered for 30 min at 110 °C and a subsequently heated
during spin coating. at 450 °C for 45 min in a muffle furnace. After that TiO2 coated FTO
glasses were kept overnight to cool down to normal room temperature
(27 °C) to use it further. In our newly developed dual-step annealing
recent advancement of the low dimensional photoelectronic materials
engineering approach, a TiO2 coated FTO glass substrate was heated at
could boost the commercialization of perovskite solar cells in near fu-
60 °C for 10 min on oven and the reddish-brown CH3NH3PbI3 precursor
ture [25–35].
solution was spin coated immediately on top of that hot substrate for
In this research work, a high efficient, dense, well-crystallize, almost
30 s at 3000 rpm followed by annealing at 80 °C for 30 min under
pin-hole free, smooth perovskite solar cell (CH3NH3PbI3) has been
normal atmospheric condition. The use of heat energy before spin
fabricated using one-step spin-coating approach with adopting a newly
coating is the best innovative part in our newly developed dual-step
derived dual-step thermal engineering technique at ambient condition
annealing engineering technique. Again CH3NH3PbI3 film was spin
unlike at nitrogen (N2) atmosphere. The CH3NH3PbI3 thin film spun up
coated using reddish-brown CH3NH3PbI3 precursor solution at
on the hot substrate and a subsequent heat treatment has been per-
3000 rpm for 45 s on top of normal TiO2 coated FTO substrate followed
formed after spin coating in this newly developed dual-step thermal
by annealed at 120 °C for 60 min under normal atmospheric condition.
engineering approach. This attractive and beneficial technique works
Finally, copper thiocyanate (CuSCN) (99% pure, Sigma Aldrich) layer
efficiently and converts perovskite precursor solution into CH3NH3PbI3
was deposited as hole transporting material (HTM) on top of both
thin film utilizing kinetic energy used during spin coating. Epitaxial
CH3NH3PbI3 perovskite devices accordingly followed by recent litera-
growth starts instantly during spin coating and few foundation layers of
ture [21,36]. Fig. 2 represents the fabricated devices structure with
perovskite materials (CH3NH3PbI3) developed which drives the high-
electrical and photo response properties of FTO/TiO2/CH3NH3PbI3/
quality, smooth and dense perovskite thin film ultimately. The epitaxial
CuSCN/Ag based solar cells using dual step annealing and conventional
growth and the formation of baseline CH3NH3PbI3 perovskite materials
annealing engineering.
are portrayed in Fig. 1. The figure is describing the formation of epi-
taxial growth of CH3NH3PbI3 film over hot substrate during spin
2.3. Characterization
coating which is the most fundamental and powerful intrinsic features
of this dual-step thermal engineering technique that builds the foun-
Field Emission Scanning Electron Microscopy (JEOL JSM-7600F)
dation of a high efficient solar device at air atmosphere.
and Scanning Electron Microscopy (Zeiss EVO MA10) were performed
to evaluate the morphologies of the CH3NH3PbI3 perovskite films. To
understand the presence of defect densities and disorder, UV/Vis
2. Experimental section
Spectrophotometer (Hitachi spectrophotometer U-4100, range:
240–2600 nm) was used to execute the UV–vis absorption spectro-
2.1. Preparation of CH3NH3PbI3 precursor solution
scopies, light absorption tendency and investigate the Urbach energy
(EU). The crystallinity and phase formation of the perovskite films were
0.3 mol (40 mL) hydroiodic acid (57 wt% in water, 99.95% pure,
recognized by an X-ray diffraction (XRD) characterizing tool (Philips
Sigma Aldrich) and equimolar methylamine (38 mL) (33 wt% in abso-
Analytical PW 3050/60X’Pert Pro) equipped with Cu Kα X-ray
lute ethanol, ≥ 99.0% pure, Sigma Aldrich) were mixed in 100 mL
(1.540 Å) source. Finally the photovoltaic performances of the
ethanol (99.9% pure, Changshu Hongsheng Fine Chemical) with con-
CH3NH3PbI3 based photovoltaic devices were carried out by means of
tinuous stirring at 1200 rpm in an ice bath for 2 h followed by evapo-
current-voltage characterization and incident photon-to-current con-
rated at 60 °C with continuous stirring at 1200 rpm until it completely
version efficiency (IPCE). The current-voltage characterization was
forms white precipitation of CH3NH3I. The crystallite CH3NH3I was
carried out through 2450 Keithley programmable source meter and
washed properly using diethyl ether [(C2H5)O] (≥ 99.7% pure, Merck
Zolix (HPS-300XA) solar simulator under AM 1.5 G condition (1 Sun
Specialities Pvt. Ltd.) with continuous stirring at 1200 rpm for 45 min
illumination, 100 mW cm−2) and the IPCE was measured under a
and repeated same the step for three times and finally dried at 70 °C in
commercial setup (IPCE measurement system, PEC- S20, Peccell
an hot air oven (Laboratory Hot Air Oven, B.C Chatterjee & Co.) for
Technologies, Japan).
overnight. An equimolar amount (1:1 mol ratio) of methylammonium
iodide (CH3NH3I) and commercially bought lead (II) iodide powder,
3. Result and discussion
PbI2 (99% pure, Sigma Aldrich) were mixed in organic di-
methylformamide (DMF) solvent (99.8% pure, Merck Specialities Pvt.
3.1. X-ray diffraction (XRD) studies
Ltd.) and stirred for 10 h at room temperature to obtain reddish-brown
methylamine lead iodide (CH3NH3PbI3) precursor solution followed by
XRD pattern of the CH3NH3PbI3 perovskite film, Fig. 3(a-c), fabri-
filtered with Whatman filter paper (0.45 µm pore PVDF syringe filter).
cated by different annealing techniques ensure the desire CH3NH3PbI3
perovskite formation by diffraction peaks originate at 14.1°, 28.4°,
43.2°, and 58.9° which are refers to the (110), (220), (330), and (440)

146
S.A. Moyez, S. Roy
Fig. 2. The devices structure of the CH3NH3PbI3 perovskite solar cell fabricated by (c) dual-step annealing engineering and (d) conventional annealing engineering.
(c) The maximum achieved photovoltaic performance and (d) the achieved IPCE of the CH3NH3PbI3 perovskite solar cell.
planes of tetragonal crystal structure respectively [37]. It is observed
significantly from the XRD resultant figure is that the film by dual-step
thermal engineering is free from any impurity trace whereas some
impure phases are present in case of conventional annealing and the
film by epitaxial growth on hot substrate after spin coating. Refinement
analysis of the conventional annealing confirms that diffraction peaks
at 12.7⁰ and 41.68⁰ belongs to the excess PbI2 phases and those two
peaks are appeared from (001) and (112) planes of hexagonal crystal
system (Fig. 3(a)). The presence of PbI2 in fabricated device can affects
the overall performances of CH3NH3PbI3 photovoltaic negatively which
occurs due to the degradation of active perovskite layer [38] and the
final film prepared by conventional annealing cannot find a way to
recompense the created damage. Only dual-step thermal engineering
(Fig. 3(b)) establishes pure perovskite (CH3NH3PbI3) phases at their
corresponding diffraction angles (14.1°, 28.4°, 43.2°, and 58.9°) without
any impurity traces. It was interestingly observed that though
CH3NH3PbI3 have been achieved for all this film but dual-step thermal
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Solar Energy Materials and Solar Cells 185 (2018) 145–152
engineering technique strengthens these peaks in higher magnitude
comparatively which can be assigned for high purity and ample amount
of perovskite formation. Whereas the weaken phase intensity of
CH3NH3PbI3 perovskite phases together with some PbI2 impurity traces
with residual precursor solution suggests that the film is degraded
quality in case of conventional annealing. The XRD study of the per-
ovskite epitaxial layer compacted on hot substrate after spin coating
(Fig. 3(c)) is very significant to understand the influences of thermal
energy and the fundamental inimitability of this newly developed dual-
step thermal engineering technique.
In this experiment further heating at 60 °C before spin coating for
dual-step thermal engineering technique plays a significant role to en-
counter the challenge of CH3NH3PbI3 formation at ambient condition.
The role of thermal energy used in this technique is portrayed in
Fig. 3(d-f) and consequent occurrences are described by Eqs. (1)–(5).
The immediately attached precursor solution over the hot substrate
annealed to sufficient degree and assembled few perovskite layers
Fig. 3. (a) XRD of the CH3NH3PbI3 thin film
prepared by conventional annealing technique,
(b) XRD of the CH3NH3PbI3 thin film prepared
by dual-step thermal engineering, (c) XRD of
the CH3NH3PbI3 perovskite epitaxial layer
with intermediate phase and precursor solu-
tion assembled on hot substrate after spin
coating, (d) Formation of the base perovskite
(CH3NH3PbI3) layer by epitaxial growth
manner during spin coating on hot substrate,
(e) Presence of epitaxial perovskite stratum
(CH3NH3PbI3), intermediate phase and pre-
cursor solution after spin coating on substrate
and (f) Fabrication of perovskite thin film
(CH3NH3PbI3) after final annealing by the
dual-step thermal engineering method.
S.A. Moyez, S. Roy
during spin coating over the substrate by epitaxial growth fashion uti-
lizing the kinetic energy of the substrate which acts as base-layers as
shown in Fig. 3(d) and by Eq. (1). The immediately formed epitaxial
layer of CH3NH3PbI3 perovskite material during spin coating glued
immensely to the hot substrate and rest precursor perovskite liquids are
consequently deposited onto that base layer gradually. A little amount
of precursor solution forms an intermediate mixture of ammonium lead
iodide (NH4PbI3) due to heat deficiency beyond a certain limit above
hot substrate. Our refinement study confirms the presence of NH4PbI3
by diffraction peak at 23.14⁰ (2θ) which can be assigned to the (203)
peak of orthorhombic crystal and 12.7⁰, 41.68⁰, and 52.38⁰ (2θ) con-
firms the presence of PbI2 phases which assigned the (001), (112) and
(008) peaks respectively of hexagonal system (Fig. 3(c)). The remnant
precursor solution remains as unreacted over this compacted epitaxial
perovskite growth along with the intermediate phase when thermal
energy vanishes absolutely. All these intermediate mixture and pre-
cursor solution gets completely converted to pure CH3NH3PbI3 per-
ovskite phase when final annealing is done at 80 °C in ambient condi-
tion, (Fig. 3(f) and Fig. 3(b)). Intermediate phase, NH4PbI3, plays a
noteworthy role to compensate the degradation of the thin film by re-
acting with CH3NH2 by Eq. (2) which generates due to the degradation
of the CH3NH3PbI3 film similar as conventional annealing [39].
NH4PbI3 rejoin with CH3NH2 and converts completely to CH3NH3PbI3
during annealing at 80 °C similarly as reference [40] while NH3 pro-
duce as a byproduct (Eq. (3)). The resultant HI appears during de-
gradation of the film combines with impure PbI2 phases along with
CH3NH2 and form desire CH3NH3PbI3 perovskite material by Eq. (4).
The remnant precursor solution over the epitaxial layer converts to
CH3NH3PbI3 while heating at 80 °C during final annealing by a simple
conversion reaction (Eq. (5)). Hence, the dual-step thermal engineering
technique developed by us comprises positive impact on CH3NH3PbI3
perovskite thin film fabrication in open air atmosphere without any
impurity traces in final device whereas conventional annealing faces
show degradation and impure traces in the final CH3NH3PbI3 device.
CH3NH3I + PbI2→CH3NH3PbI3 (1)
CH3NH3I→CH3NH2 + HI (2)
NH4PbI3+ CH3NH2→CH3NH3PbI3 + NH3 (3)
CH3NH2+ HI + PbI2→CH3NH3PbI3 (4)
CH3NH3I + PbI2→CH3NH3PbI3 (5)
3.2. Morphology study
Morphology of CH3NH3PbI3 perovskite films fabricated through
different annealing conditions have been studied under scanning elec-
tron microscope (SEM) characterizing technique as shown in Fig. 4(a-
b). This morphology study exhibited that the perovskite thin film fab-
ricated by dual-step thermal engineering technique has been formed
compact, dense, uniform and almost pinholes free perovskite whereas
the CH3NH3PbI3 perovskite thin film by conventional annealing has
been comprised of several small needles and scattered orientation of
CH3NH3PbI3 perovskite island observed throughout the whole substrate
which drives low surface coverage, non-homogeneous and unhealthy
perovskite film. The SEM images also reveals that the perovskite film by
dual-step thermal engineering contains many platelets of 30–40 nm in
radius and several flat tableted units of 100 nm in length and 40–50 nm
in width and these nano units has compactly been locked together
which leads to a compact and dense thin film whereas enormous
numbers of trap states and non-continuous cavities, in case of con-
ventional annealing, weakens the film morphology. Solar spectrum will
easily pass directly without being absorbed through these broad gap
associate to this interrupt film that could made negative impact on the
performance for the device fabricated by the conventional annealing.
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Solar Energy Materials and Solar Cells 185 (2018) 145–152
The presence of pinholes or gaps may serve as trap states or re-
combination centre and it will resist the carrier mobility within the
CH3NH3PbI3 perovskite film by conventionally annealed while the film
by dual-step thermal engineering is far beyond these limitations.
Surface tension of the precursor solution significantly affects the
morphology and can play an intrinsic role for the formation of rough-
ness for final film as portrayed in Fig. 4(c-d). Surface tension becomes
active in large dimension after the end of spin coating and it induced
until the nucleation of CH3NH3PbI3 phase started to occur. In case of
conventional annealing, surface tension shrinks the precursor solution
to their enforced or insisted direction hence the precursor solution
coalescence or gather to some extent to droplets at some specific re-
gions of the substrate (Fig. 4(d), step 1–2) and it introduces some gaps
or pinholes to the precursor film after spin coating. The subsequent
annealing at 120 °C after spin coating vaporizes the organic solvent of
precursor solution and the nucleation of perovskite crystallite initiate.
Naturally the morphology of the final CH3NH3PbI3 perovskite film lost
its uniformity when it annealed completely and hence interruption
along with pinhole appears for final film for conventional annealing
engineering (Fig. 4(d), step 3). The morphology of the film fabricated
by dual-step thermal engineering is far beyond this drawback. In this
method, the precursor solution spin coated on a hot substrate and the
heat energy act as an adhesive or anchoring agent for final perovskite
film. The epitaxial growth started to occurs during spin coating utilizing
the kinetic energy of the substrate and it assembled few CH3NH3PbI3
perovskite layers compactly over the substrate which lowers the prob-
ability of interruption or pinholes in the final film (Fig. 4(c), step 1).
The intermediate mixture formed further when kinetic energy become
low and it placed automatically over the epitaxial layer. The unreacted
precursor solution beyond heat limit over hot substrate positioned them
parallel to horizon or perpendicular to vertical in the cavity of epitaxial
layer by its default liquidity property. The surface tension of the pre-
cursor solution, in this case, becomes inactive though it remains present
(Fig. 4(c), step 2) because the cavity embanking the precursor solution
at their acquired place. The formation of intermediate phase and rem-
nant unreacted perovskite solution after spin coating has already been
discussed in XRD section. Overlying precursor solution recompenses
easily if any interruption in-between epitaxial layer of CH3NH3PbI3
occurs because overlying precursor solution can penetrate those gaps
and fill them. Final annealing, at 80 °C, converts all those intermediate
mixture and precursor solution completely to coveted perovskite
CH3NH3PbI3 easily and a smooth, uniform, compact and almost pinhole
free film develops (Fig. 4(c), step 3). So, the epitaxial CH3NH3PbI3
layer forms for dual-step thermal engineering technique during spin
coating lowers the pinhole formation and recombination centre while
the film by conventional annealing is not free from pinholes, trap states
and defects or roughness.
3.3. Ultraviolet-visible (UV–Vis) absorption spectroscopy
Light interaction fundamentals and spectrum absorbing propensity
of the CH3NH3PbI3 perovskite film fabricated by different annealing
technique have been explored using the ultraviolet-visible (UV–vis)
absorption spectroscopy as shown in Fig. 5(a). The resemblance in
absorbance of the samples prepared through dual-step thermal en-
gineering and conventional annealing technique with previous research
works over the spectrum range of 400–800 nm, confirming the forma-
tion of CH3NH3PbI3 with the bandgap of 1.5 eV [41,42]. It is clear from
the Fig. 5(a) that dual-step thermal engineering has comparatively
large absorbance to the conventional annealing throughout the entire
spectrum and the absorption coefficient (α) values of the both films,
Fig. 5(b), solely supports this agreement. The film fabricated by dual-
step thermal engineering have more than 1.5-time absorption coeffi-
cient (α) value in the order of 104 cm−1 scale at their peak point. The
discontinuous morphology of the film by conventional annealing causes
low optical absorption because the solar spectrum can pass
S.A. Moyez, S. Roy
straightforwardly through this interrupt film or pinholes without being
absorbed completely whereas the compacted, assembled and con-
tinuous perovskite film (CH3NH3PbI3) by dual-step thermal engineering
have greater absorbance affinity. A notable absorption declination is
detected in UV–vis spectrum in the spectrum range between 400 and
450 nm which confirms the existence of PbI2 [43] in case of the film
fabricated by conventional. In addition, another representative absor-
bance peak near the 500 nm is further highlighted the presence of PbI2
for the same film while the film of dual-step thermal engineering has no
such additional impure absorbance neck formation [17]. This is well-
agreed with the XRD analysis too.
3.4. Urbach energy (EU)
The presence of defects densities, disorders, impurities and the
nature of crystallinity of a semiconducting thin film can be explored
from UV–vis spectrum beside its light absorption analysis. The optical
absorption spectrum is correlated with these qualitative natures of
semiconducting thin film via Urbach energy (EU). Absorption
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Solar Energy Materials and Solar Cells 185 (2018) 145–152
Fig. 4. SEM morphology images of (a)
CH3NH3PbI3 perovskite film fabricated by
dual-step thermal engineering technique, (b)
CH3NH3PbI3 perovskite film fabricated by
conventional annealing engineering. (c) Effect
of surface tension of precursor solution on the
morphology of CH3NH3PbI3 perovskite film
fabricated by dual-step thermal engineering,
and (d) effect of surface tension of precursor
solution on the morphology of CH3NH3PbI3
perovskite film fabricated by conventional an-
nealing.
coefficient (α) curve follows an exponential fashion (Eq. (6)) and the
part close to the optical band edge is called Urbach tail. The Urbach tail
appears in the low photon energy range and it afforded qualitative
information of a thin film semiconducting materials. The quantitative
analysis of the Urbach tail is generally known as Urbach energy (EU)
and calculated from the reciprocal value of the slope of straight line
from Fig. 6 by plotting ln(α) against the photon energy (hν) (Eq. (7)).
α = α oexp(hνEU –1) (6)
ln(α) = ln(α o) + (hνEU –1) (7)
where, αo is a constant and EU called Urbach energy, hν is the photon
energy.
The value of EU, extracted from the Fig. 6, for CH3NH3PbI3 per-
ovskite film fabricated by the dual-step thermal engineering and con-
ventional annealing are 25 meV and 41 meV respectively which is
higher than the reported value of 15 meV for CH3NH3PbI3 [44]. Higher
EU value for the film by conventional annealing recommends that there
may higher number of defects and disorders presents in the film
Fig. 5. (a) UV–vis absorption spectra of
CH3NH3PbI3 perovskite solar cell treated with
different engineering technique, dual-step
thermal engineering and conventional an-
nealing and (b) absorption coefficient (α) of
CH3NH3PbI3 perovskite solar cell fabricate
through dual-step thermal engineering tech-
nique and conventional annealing.
S.A. Moyez, S. Roy
Fig. 6. The dependence of ln(α) with photon energy (hυ) of CH3NH3PbI3 per-
ovskite film fabricated by (a) dual-step thermal engineering (b) conventional
annealing from which Urbach Energy (EU) values can be extracted.
compare to the dual-step thermal engineering because EU reflects the
disorders and defects in the semiconducting crystal [45]. It was re-
ported that the larger EU value will causes more recombination of the
exciton with faster rate and overall performance of the perovskite thin
film by conventional annealing will be degraded [46]. Thus, the EU
exploration is well-fitted with the XRD studies and morphology ana-
lysis.
3.5. Photovoltaic performance
The current-voltage (J–V) characterization and incident photon-to-
current conversion efficiency (IPCE) of CH3NH3PbI3 photovoltaic de-
vices fabricated by dual-step thermal engineering and conventional
annealing has been studied to investigate the photovoltaic perfor-
mances (Fig. 7). The current density-voltage (J–V) characterizations
Fig. 7. Graphical representation of the photovoltaic performance of the CH3NH3PbI3 perovskite photovoltaic device. Consistency performances with error bar of the
(a) short-circuit current density (JSC), (b) open circuit voltage (VOC), (c) power conversion efficiency (PCE), (d) fill factor (FF).
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Solar Energy Materials and Solar Cells 185 (2018) 145–152
were evaluated for 40 numbers of photovoltaic devices and the statis-
tical analysis with mean value and standard deviation (SD) have been
performed to understand the performance consistency (please see
Supplementary Fig. S1 and Table S1 for details) and the result of the
device achieved maximum photovoltaic performance is also included in
Fig. 2(c).
The experimentally extracted values reveals that photovoltaic de-
vice prepared by dual-step thermal engineering achieved a maximum
PCE of 12.02% along with 0.977 V open circuit voltage (VOC), and short
circuit current density of 19.13 mAcm–2 (JSC), whereas the device
fabricated by conventional annealing exhibit comparatively low per-
formance (PCE = 8.74%, VOC= 0.931 V, JSC = 14.86 mAcm–2) but
both these devices have same FF value of 0.63 (Fig. 7 and
Supplementary Table S1). Analysis of the photovoltaic parameters of
CH3NH3PbI3 perovskite device by dual-step thermal engineering con-
firm an enhancement in PCE by 37.52% over conventional annealing
for the device achieved maximum performance which endorses the
dual-step thermal engineering as an intellectual device fabrication
technique. The quality of the device for dual-step thermal engineering
is believed to be originated by proper utilization of the heat which is the
most intrinsic factor of this new technique and is confirmed by the
morphology analysis (Fig. 4), phase formation study (Fig. 3), and ab-
sorption coefficient (α) (Fig. 5(b)) value. The mean efficiency values
(mean PCE) achieved for 40 devices shows a hike of 53.30% in case of
dual-step thermal engineering (mean PCE 11.73%) over conventional
annealing (mean PCE 7.65%). The device fabricated by dual-step
thermal engineering have higher mean FF (≈ 0.65) compare to the
conventional annealing (mean FF ≈ 0.62). The higher FF suggests that
the film by conventional annealing has been driven by higher roughness
comparatively because FF is slightly influenced by the roughness [47]
of the film. The more roughness degrades the quality of the device by
recombining exciton generation and in contrast higher mean FF au-
thorizes that newly derive dual-step thermal engineering method form
higher quality device. Large open circuit voltage (VOC = 0.977 V) and
S.A. Moyez, S. Roy
short circuit current density (JSC = 19.13 mAcm–2), for device showing
maximum performances, along with their large mean value (mean VOC
= 0.956 V, and mean JSC= 18.93 mAcm–2) from 40 number of devices
for the perovskite device by dual-step thermal engineering compare to
the less open circuit voltage (VOC = 0.931 V) and current density (JSC=
14.83 mAcm–2) along with their corresponding mean value (mean VOC
= 0.898 V, mean JSC=13.64 mAcm–2) for conventional annealing is
reflected the qualitative characteristic of this new method. The details I-
V characterization result and extraction data of the same for 40 num-
bers of photovoltaic devices fabricated by both technique can find in
Supplementary Table S1 and Fig. S1.
The consistency performance of the devices fabricates by both these
techniques, Fig. 7. and Supplementary Table S1, shows that dual-step
thermal engineering has better uniformity and smooth performance
over conventional annealing. The PCE for dual-step thermal en-
gineering shows a variation in a range of 11.02–12.02% with a standard
deviation (SD) of 0.263, whereas the same for conventional annealing
device is 7.04–8.74% with a SD of 0.579. The FF for dual-step thermal
engineering exhibit narrow difference: 0.62–0.66 along with a SD of
0.011 while the devices by conventional annealing show remarkable
differences in FF performance (0.57–0.67) along with a SD of 0.028.
The dual-step thermal engineering shows small difference in JSC value
(18.47 – 19.13 mAcm–2) with a SD of 0.212 while the conventional
annealing showing the same (JSC~ 14.59 – 12.82 mAcm–2) with re-
markable SD of 0.628 but the both the technique has similarity in SD
(0.018) for VOC. The overall higher variation, i.e., higher standard de-
viation values, of all parameters including PCE, JSC, VOC and FF for
conventional annealing over dual-step thermal engineering confirms
this new technique as a very efficient, consistence and effective to
achieve a high-quality perovskite device in open atmosphere.
IPCE has been carried out for each perovskite device, fabricated by
both aforesaid methods, to investigate the performance and current
density generation by the device to validate the IV characteristic as
shown in Fig. 2(d). The IPCE characteristic clearly exhibits that the
photovoltaic device fabricated by conventional annealing has lower
incident photo-to-current conversion efficiency (IPCE) value
throughout the entire visible spectrum compare to the device by dual-
step thermal engineering and it has formed a declination neck near
620 nm which occurs due to the unhealthy film morphology and pre-
sence of defect in the CH3NH3PbI3 perovskite film. The device fabri-
cated by dual-step thermal engineering has been achieved a handsome
amount of IPCE value, above 84%, while the maximum IPCE has been
reached to 69% for device fabricated by conventional annealing but the
photocurrent conversion for both these devices has been started to
occur at 800 nm with the bandgap value of 1.55 eV for CH3NH3PbI3
material. IPCE result shows that the dual-step thermal engineering has
been achieved an integrated current density (JSC,INT) of 18.94 mAcm–2
which is reasonably similar to the mean JSC (18.93 mAcm–2) achieved
from current-voltage result but the device by conventional annealing
has been achieved a JSC,INT of 13.43 mAcm–2 is fairly similar to the JSC
from current-voltage result (13.64 mAcm–2). The calculation shows that
integrated current density (JSC,INT) has enhanced to 41.03% for dual-
step thermal engineering process over conventional annealing. Both the
current density (J-V) and IPCE characterization has been showing a
good agreement in term of current density generation and perfor-
mances.
4. Conclusion
Fabrication of CH3NH3PbI3-based perovskite photovoltaic device in
open air atmospheric condition is a big challenge. In this research work,
CH3NH3PbI3 based perovskite solar cell have been developed under the
new technique and named as dual-step thermal engineering and com-
pare with CH3NH3PbI3 photovoltaic device fabrication by conventional
engineering to validate the newly develop method. The investigation of
the characterization reveals that dual-step thermal engineering
151
Solar Energy Materials and Solar Cells 185 (2018) 145–152
significantly influences the film morphology, phase formation, optical
properties and photovoltaic parameters positively hence a remarkable
enhancement in photo conversion efficiency (37.52% for highest
achieved devices and 53.33% for mean efficiency value) and integrated
current density (JSC,INT) for IPCE (41.03%) has been achieved for
CH3NH3PbI3 photovoltaic device over conventional annealing. The
annealing temperature and/or annealing method have great influences
on perovskite solar cell formation and we recombined those influencing
factor tactfully in this novel method to overcome the challenges of
perovskite solar cell (CH3NH3PbI3) encounter in open air atmosphere.
Dual-step thermal engineering ensures qualitative CH3NH3PbI3 photo-
voltaic production and is very economical comparatively because total
annealing time and temperature required for dual-step thermal en-
gineering is far less (total time 40 min and maximum temperature 80
°C) than conventional annealing process (total time 60 min and max-
imum temperature 120 °C) though the kinetic energy is applied twice in
this newly developed method. Therefor dual-step thermal engineering
saves energy and time and it enhance the device performances si-
multaneously. Thus, our employed newly derived method named as
dual-step thermal engineering we employed here could have accelerate
the commercialization of perovskite solar cell and will move forward
the perovskite photovoltaic industry a step ahead in future.
Acknowledgements
This work is supported by Science and Engineering Research Board
(SERB) grants funded by Department of Science and Technology (DST),
Central Government of India through Fast Track Scheme for Young
Scientists (Registration no. 175/2013, SB/FT/CS-105/2013) and
University Grand Commission (UGC), India through Maulana Azad
National Fellowship (Award letter no. F1–17.1/2014-15/MANF-2014-
15-MUS-WES-47983).
Funding information
● Science and Engineering Research Board (SERB) (SB/FT/CS-105/
2013) [Roy].
● University Grand Commission (UGC), India F1-17.1/2014-15/
MANF-2014-15-MUS-WES-47983).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.solmat.2018.05.027.
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