Optical Materials 109 (2020) 110255

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Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat

Annealing time effects on the structural, morphological and optical

properties in hybrid CH3NH3PbI3 perovskites: Experimental and
ab-initio investigations
A. Natik a, R. Moubah a, *, Y. Abid a, H. Zaari b, H. El Moussaoui c, Y. Tamraoui d, M. Abid e,
H. Lassri a
a
LPMMAT, Hassan II University of Casablanca, Faculté des Sciences Ain Chock, BP 5366, Mâarif, Casablanca, Morocco
b
LaMCScI, Faculty of Science, Mohammed V University, B.P 1014, Rabat, Morocco
c
Institute of Nanomaterials and Nanotechnologies, Materials and Nanomaterials Center, MAScIR Foundation, B.P 10100, Rabat, Morocco
d
Materials Science and Nanoengineering Department (MSN), Mohammed VI Polytechnic University (UM6P), Lot 660 – Hay Moulay Rachid, Benguerir, 43150, Morocco
e
LPTA, Faculté des Sciences Ain Chock, Hassan II University of Casablanca, Casablanca, Morocco

A R T I C L E I N F O A B S T R A C T

Keywords: We report on the effects of annealing time on the structural, morphological and optical properties of hybrid
Hybrid perovskites CH3NH3PbI3 perovskite powders. X-ray diffraction analysis confirms the tetragonal structure. We demonstrate a
Structural properties conversion of the intermediate phase into perovskite phase with increasing annealing time. Higher purity in
Optical properties
which the intermediate phase undergoes a complete transition to perovskite was obtained after annealing time of
ab-initio calculations
4 h at a temperature of 110 ◦ C. The crystallite size increases with increasing annealing time. Scanning electron
microscope allows to observe micro-sticks, in which their diameters increases with increasing annealing time.
The optical properties of hybrid perovskite were studied using UV–visible spectroscopy and ab-initio calcula­
tions. The band gap energy decreases, while the refractive index increases with increasing annealing time. These
changes can be understood by the decrease of lattice parameters with increasing annealing times, as supported by
ab-initio calculations.

1. Introduction materials comes from several factors: the ease of their synthesis, their
low cost and their integration into a photovoltaic architecture. The
Halide perovskites (HP) have revolutionized the photovoltaic field power conversion efficiency (PCE) yield for perovskite-based solar cells
over the past decade. These materials are very interesting for the next could rise to 31% [4], which exceeds that of silicon cells. Hybrid pe­
generation of solar cells, in which electrical conductivity and mobility rovskites are semiconductor molecular crystals containing an organic
are good which are two essential parameters to transform solar energy and an inorganic part, obtained by self-assembly when deposited in a
into electricity [1]. In addition, the low cost of perovskites and the ease spinner on a substrate [5]. Perovskites of the CH3NH3PbI3 type have
of their synthesis are the main advantages of halide perovskite cells, very good conduction properties and an optical gap to collect the
making them an interesting promising alternative to the high cost of wavelengths of the solar spectrum, so it is very well suited for photo­
silicon. These compounds have a general formula of the form AMX3 [2] voltaic applications [6]. In order to exploit these materials in techno­
where M is a divalent ion which can be Pb2+, Cu2+, Sn2+, Co2+, Fe2+, logical applications a deep understanding of the influences of
Mn2+, Cr2+, Ge2+, Eu2+, Cd2+or Yb2+, and X is halogen. A is a cation that preparation techniques and preparation conditions is required. In this
can be an inorganic cation such as Cs+ for example or an organic cation work, we report on the annealing time effects on the structural,
such as ammonium (CH3NH+ 3 = MA) [3]. Many research activities were morphological and optical properties of hybrid perovskite CH3NH3PbI3
devoted to improve the efficiency of photovoltaic and light-emitting powders annealed at 110 ◦ C by combining experimental and ab-initio
devices containing these materials. Applications based on MAPbI3 calculations investigations.
hybrid perovskites have flourished in recent years. The interest of these

* Corresponding author.
E-mail address: [email protected] (R. Moubah).

https://doi.org/10.1016/j.optmat.2020.110255
Received 19 June 2020; Received in revised form 18 July 2020; Accepted 21 July 2020
0925-3467/© 2020 Elsevier B.V. All rights reserved.
A. Natik et al. Optical Materials 109 (2020) 110255

2. Experimental details they did not completely disappeared, indicating that a stable interme­
diate phase existed between duration 1 h and 3 h annealing times. In
To prepare the perovskite precursor solution CH3NH3PbI3, stoi­ order to obtain higher purity perovskite, the synthesis conditions under
chiometric amounts of PbI2 and CH3NH3I were dissolved N, N dime­ which the intermediate phase can undergo a complete transition to
thylformamide DMF at 60 ◦ C by stirring vigorously during 10 h. The perovskite were examined. Indeed, the heat treatment of perovskites at
obtained solution is homogeneous and yellow in color (color of the 110 ◦ C during 4 h exhibits a much higher purity. The intermediate phase
starting material PbI2). Then, they were annealed at a temperature of completely converted to perovskite at that time and there were no in­
110 ◦ C at different times (1 h, 3 h and 4 h). A color variation of the termediate phases left. Preferential orientation along the direction (110)
samples is obtained, it changes from light grey to dark grey during the and (220) was observed in samples prepared at 110 ◦ C. This was also
duration 1 h, 3 h respectively then it has become black for a duration of observed by Guo et al. [11]. The longer heating time has a positive
4 h. We ground each sample, before each X-ray diffraction (XRD) mea­ impact on the formation of oriented perovskite. This indicates that the
surement. Characterization was performed using a BRUKER powder effect of heat treatment is obvious, to convert all reagents into a product
diffractometer, with Cu Kα radiation at room temperature and 40 mA in with a desirable chemical composition. The double peak appearing in
5–80◦ 2θ range with a scan step of 0.0105◦ . Optical measurements were the crystal plane of the (220) peak of the XRD patterns is due to a
carried out using PerkinElmer LAMBDA™ 1050 UV/Vis/NIR spec­ transition from the tetragonal to the cubic phase with a double texture
trometer equipped with an integrating sphere in the range of 250–1500 [004]/[220] corresponding to energy stable states. This ferroelastic
nm with 1 nm interval in order to accurately find out the optical ab­ transition is due to the existence of stresses induced by the effect of
sorption edge in UV–vis–near infrared. Investigation of electronic and annealing, causing domains of different orientations to appear, the in­
optical properties of CH3NH3PbI3 was also investigated by the use of tensity of the (220) peak being amplified with the duration of the
density functional theory (DFT) based on the full potential linearized annealing time. This property is generally associated with ferroic
augmented plane wave (FP-LAPW) [7] using Perdew–Burke–Ernzerhof properties. Lattice parameters for a tetragonal phase were calculated
generalized gradient approximation PBE-GGA [8] implemented in using the following formula d1​ = h a+k
2
2
2 2
+ cl 2 [12]. We have found that
WIEN2k computational code [9]. Thus, the generalized gradient both the a and c lattice parameters decrease with the increase annealing
approximation coupled with spin–orbit coupling (SOC) (GGA + SOC) time, this may be due to the fact that the perovskite prepared at 110 ◦ C
was also included in calculations. The two calculation methods were can exhibit a certain number of defects such as intermediate phase
used to support the experimental results. particles, lattice disturbances, etc. Annealing at different times removes
the intermediate phase particles and therefore the lattice reduction. The
3. Results and discussion lattice parameters were summarized in Table 1 for the three samples (S1,
S2, S3) annealed respectively at (1 h, 3 h and 4 h).
X-ray diffraction patterns of MAPbI3 powders annealed at different The crystallite size was calculated using the Debye-Scherrer formula
times (1 h, 3 h and 4 h) were displayed in Fig. 1, which show different Kλ
( D = β ​ cos ​ θ) [13] where K is the shape factor having value of ~0.9, λ is
diffraction peaks. From these diffractograms, we identified a tetragonal
the X-ray wavelength, β is the Full-Width at Half-Maximum and θ is the
structure (I4/mcm) at room temperature.
Bragg angle. The crystallite size, first it increases approximately from
Typical peaks at 14.10◦ , 19.99◦ , 23.47◦ , 24.47◦ , 28.14◦ , 28.42◦ ,
30.305 to 36.342, then stabilizes at 36.350 nm, for 1 h, 3 h, and 4 h
30.89◦ , 31.61◦ , 31.8◦ are attributed respectively to the plans (110),
annealing times, respectively. One can notice that the intermediate
(200), (211), (202), (004), (220), (213), (114) and (310) of perovskite
phase particles can modify the crystallite size when the annealing time
CH3NH3PbI3. For the annealing times of 1 and 3 h, the XRD diffracto­
changes. These particles have a great influence on the kinetics, and the
grams reveal the presence of intermediate phases, which are the PbI2-
crystallization texture. The crystallite size values were summarized in
DMF complex, the PbI2-MAI-DMF complex, and the CH3NH3PbI3⋅H2O or
Table 1 for the three samples (S1, S2, S3) annealed respectively at (1 h,
dehydrated (CH3NH3)4PbI6⋅2H2O monohydrate compound [10]. It can
3 h and 4 h).
be observed that the 1 h annealing has intense intermediate phase peaks.
Fig. 2a) and b), and c) show the SEM images of MAPbI3 prepared at
As a consequence, this annealing time does not allow the reagents to be
110 ◦ C at 3 different annealing times. The SEM images of MAPbI3 were
converted into the desired phase. With increasing annealing time to 3 h,
analyzed to better understand the impact of annealing time on the
the intensity of peaks of the intermediate phase diminished. However,
MAPbI3 morphology. The particles of the latter have a structure in the
form of micro-sticks. But they have been grouped into large, non-
homogeneous agglomerates; they are not uniform in length and thick­
ness both for the same annealing time and for different annealing times.
The particles of the latter have a structure in the form of micro-sticks.
The dimensions and morphologies of perovskite particles depend on
the synthesis parameters and the types of precursors used then the re­
action and particle growth stages, which determine the morphology of
particles. However, it can be seen from the SEM that the organic matter

Table 1
Lattice parameters, Crystallite sizes and band gap of CH3NH3PbI3 annealed at
different times. Eg obtained using ab-intio calculations were determined by
introducing the experimental lattice parameters into the calculations.
Sample Lattice Crystallite Eg Eg Eg
parameters (Å) sizes (nm) (Exp) (GGA) (GGA+SOC)

S1 (1 a=b= 8.93, 30.305 1.53 1.71 0.84

h) c=12.68
Fig. 1. X-ray diffraction (XRD) of MAPbI3 heated at 110 ◦ C during: a) 1 h, S2 (3 a=b= 8.90, 36.342 1.52 1.68 0.78
(Symbols are used to Identify MAPbI3 and the composition of the intermediate h) c=12.68
S3 (4 a=b= 8.85, c= 36.350 1.50 1.64 0.75
phase), b) sample of MAPbI3 annealing at 3 h. While c) shows the sample
h) 12.65
MAPbI3 annealed at 4 h (star patterns shows pure perovskite).

2
A. Natik et al. Optical Materials 109 (2020) 110255

Fig. 2. SEM images of MAPbI3 annealed at 110 ◦ C during a) 1 Hour, b) 3 Hours, c) 4 Hours.

Fig. 3. a) Optical reflectance spectra of the MAPbI3 perovskite as a function of annealing time, b) Optical absorption spectra, c) (F(R)*hυ)2 plots.

3
A. Natik et al. Optical Materials 109 (2020) 110255

of intermediate phase located around the large grains and with the in­ disturbances in the electronic structure of atoms, ions or molecules. One
crease in annealing time it begins to disappear until it is completely or more electrons absorb this energy to jump from a low energy level to a
converted into pure perovskite (Fig. 2(c)). In comparison, MAPbI3 higher energy level. However, since the formation of the prohibited
samples are composed of micro-sticks of different sizes. We cannot bands is due to the regularity of the crystal structure, any disturbance of
compare the length because of the grinding effect, but we can compare the latter tends to create accessible states within these prohibited bands,
their thickness as a function of the annealing time. These micro-sticks making the gap more “permeable” then the longer the annealing time
have an average diameter increases from 1.43 to 1.49 μm for anneal­ increases the more the structure becomes more and more ordered. From
ing time 1 h, 4 h respectively. The change in the diameters of the micro- Fig. 3(c), the perovskite MAPbI3 optical band gap can be calculated from
sticks was observed during the increase in annealing time, which is in the UV–Vis spectra in diffuse reflectance mode. Using the Kubelka-Munk
line with the XRD analysis. formalism F(R) [15].
Spectrophotometric methods are the most commonly used tech­
niques to provide information on the optical properties of the sample to α (1 ​ − ​ R)2
= F(R) =
be analyzed, such as light transmission, absorption, optical gap esti­ S 2R
mation, etc,. In this study, the main focus was on the study of the evo­ Where, R is the reflectance, α is the absorption coefficient and S is the
lution of optical absorbance, optical reflectance, refractive index and diffusion coefficient. The optical bandgap was calculated using Tauc
energy gap as a function of the annealing time at a temperature of 110 plot, as shown in Fig. 3(c). The plot of (F(R)*hν) 2 against hν gives rise
◦
C. the values of Eg by extrapolating the linear variation to (F(R)*hν) 2 = 0.
Fig. 3(a) shows the reflectance spectra of MAPbI3 for different We have observed experimentally that the optical band gap of perov­
annealing times. We notice that the reflectance is low in the visible re­ skite decreases slightly with the increase in the annealing time of 1.53,
gion, and from 800 nm onwards, the reflectance spectra increase 1.52 1.50 eV, which can be explained by the decrease in the lattice
rapidly, then become almost constant in the infrared. parameter, as was observed by the XRD analysis. This can be supported
Fig. 4(b) shows the evolution of the optical absorption spectrum of by ab-initio calculations Fig. 4. The calculated band gap energies were
MAPbI3 at different annealing times. We notice that the different sam­ obtained by changing the lattice parameters (different annealing times)
ples show an increasingly high absorption in the visible area. We can of CH3NH3PbI3. As can be observed (Table 1), by introducing a decrease
also see in this figure the appearance of a pronounced variation in the in lattice parameters in ab-initio calculations we found that the band gap
absorption front; this variation is the signature of excitonic effects [14]. energy decreases. The calculated and experimental band gap energies
The beginning of optical absorption passed to lower energies with the are summarized in Table 1. Although there are some differences be­
increase in annealing time. Indeed, the absorbed energy causes tween the calculated and experimental band gap energies, the change of
calculated band gap energies without SOC is in agreement with the
experimental results. This was also reported by other authors [16]. We
note that the inclusion of spin orbit coupling into calculations does allow
an accurate determination of band gap energy. The negligence of SOC
raises the band gap values to the correct values close to the experimental
values as well as to reduce the computation time [17–19].
By the use of the Wemple-DiDomenico model [20], the refractive
index of the halide perovskites should be simply related to the bandgap
via the simple relationship:

n2 ≈ 1 + 8.32 eV /Eg

We have experimentally obtained 2.53, 2.54 and 2.55 for annealing

times of 1 h, 3 h and 4 h, respectively. An increase in refractive index is
observed with increasing annealing time, which can be supported by the
theoretical calculation. The static refractive index using the approxi­
mation (GGA + SOC), was found to be 2.45, 2.49 and 2.61 for the three
samples (S1, S2, S3) annealed respectively at (1 h, 3 h and 4 h). Table 2
shows the calculated and experimental refractive index for the three
samples. It can then be seen that the theoretical study is in good
agreement with the experimental one, and that a small energy gap gives
a high value of the refractive index which increases further with the
increase in annealing time.
The increase with refractive index with annealing time can be
undetrood by the increase of density (Table 2). As can be observed the
density increases with increasing annealing time; the densification is
greater after an annealing time of 4 h. The densification could be mainly
related to the release of particles from the intermediate phase [21], or
attributed to the virtual elimination of microcracks in successive an­
neals; consequently, the bonding bridges between the grains perovskite

Table 2
Refractive index and the density of CH3NH3PbI3.
Sample Refractive index Refractive index density (g/
(Exp) (Theo) cm3)

S1 2.53 2.45 4.07

S2 2.54 2.49 4.09
Fig. 4. Computed DOS of CH3NH3PbI3 using the approximation a) GGA,b)
S3 2.55 2.61 4.15
GGA + SOC.

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A. Natik et al. Optical Materials 109 (2020) 110255

will be improved, and therefore the bonds between these grains can be the work reported in this paper.
strengthened [22]. This result indicates that the annealing time can
induce a denser material with desirable mechanical properties. References

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The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence