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Phase transition kinetics and surface binding


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states of methylammonium lead iodide


Cite this: DOI: 10.1039/c5cp06232b
perovskite
G. Rajendra Kumar,a A. Dennyson Savariraj,a S. N. Karthick,a S. Selvam,a
B. Balamuralitharan,a Hee-Je Kim,a K. K. Viswanathan,b M. Vijaykumarc and
Kandasamy Prabakar*ac

We have presented a detailed analysis of the phase transition kinetics and binding energy states of solution
processed methylammonium lead iodide (MAPbI3) thin films prepared at ambient conditions and annealed
at dierent elevated temperatures. It is the processing temperature and environmental conditions that
Received 14th October 2015, predominantly control the crystal structure and surface morphology of MAPbI3 thin films. The structural
Accepted 7th February 2016 transformation from tetragonal to cubic occurs at 60 1C with a 30 minute annealing time while the 10 minute
DOI: 10.1039/c5cp06232b annealed films posses a tetragonal crystal structure. The transformed phase is greatly intact even at the
higher annealing temperature of 150 1C and after a time of 2 hours. The charge transfer interaction
www.rsc.org/pccp between the Pb 4f and I 3d oxidation states is quantified using XPS.

1. Introduction Perovskite solar cells have emerged as leaders in photovoltaic


technologies and seem to contribute to large scale solar energy
The worlds energy consumption is moving towards renewable production due to their high PCEs and compatibility with
energy resources, mainly solar energy due to environmental con- scalable processes and are a promising alternative to conven-
cerns related to global warming and sustainability. The challenge tional silicon solar cells.7 Especially the MAPbI3 perovskite light
has always been the conversion of solar energy into electrical energy harvester, as having a direct band gap of about 1.451.6 eV, high
in an ecient and cost-eective way. Though crystalline silicon carrier mobility, large absorption coefficients and the ability to
dominates the photovoltaic industry with eciencies over 20%, it form very high quality crystals rapidly at low temperature are
remains relatively expensive to manufacture.1 In silicon photo- added advantages.8 The introduction of MAPbI3 as a sensitizer in
voltaics, the substantial reduction of the manufacturing cost is electrolyte based dye-sensitized solar cells (DSSCs) was marked
highly required to assure the mass production and to fulfil future as the beginning of perovskite-based photovoltaic technology.9
energy consumption demands.2 Recently, single or multiple solution Consequently, the planar heterojunctions and mesoscopic metal
processes have been introduced to fabricate dye-sensitized,3 oxide structured solar cells start with increased efficiency.10 Since
quantum dot,4 and polymer solar cells5 at low temperatures the first work published on MAPbI3 perovskites, a set of prominent
and the manufacturing cost of these cells are cheaper than ideas have been stimulated over past few years with different
silicon cells; however, they still suer from long-term stability feasible methodologies focused only on achieving higher efficiency,
and low power conversion eciency (PCE) as a result of funda- but lacking identification of the cause of perovskite degradation
mental energy losses occurring at the heterojunction interface.6 when exposed to air.11,12
The hygroscopic nature of the methylammonium (MA) cation
traps moisture from the air which increases the crystal size along
a
Department of Electrical and Computer Engineering, Pusan National University,
with causing contamination. However, moisture is not the only
San 30, Jangjeong-Dong, Gumjeong-Ku, Busan-609 735, South Korea.
E-mail: prabakar@pusan.ac.kr, kprabakar@gmail.com
problem for degradation, even perovskite devices processed in
b
UTM Centre for Industrial and Applied Mathematics, Ibnu Sina Institute for an inert (N2) atmosphere also undergo destabilization.12,13 The
Scientific & Industrial Research, Department of Mathematical Sciences, Faculty of device interface may also play a crucial role in the degradation
Science, Universiti Teknologi Malaysia, Johor Bahru, 81310, Johor, Malaysia mechanism.14 This issue has grown as a big concern for fabri-
c
Pacific Northwest National Laboratory (PNNL), Richland, WA-99354, USA
cating perovskite-based photovoltaic devices on a large scale. It is
Electronic supplementary information (ESI) available: Scherrers formula to
calculate grain size, XPS survey spectra with elemental concentration, estimation
mainly due to a lack of understanding of their physical proper-
of the atomic percentage of C 1s, O 1s, and N 1s using the AM-RSFs method. See ties. In this work, we have intensely focused on investigating the
DOI: 10.1039/c5cp06232b phase transition kinetics and surface binding states of MAPbI3

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thin films prepared at ambient conditions and processed at


dierent temperatures such as 60 1C, 100 1C, and 150 1C and
tried to understand the real issues aecting the perovskite over
the fundamental physical properties, beyond the concern of
photovoltaic eciency. Here, we report a MAPbI3 thin film
prepared on a fluorine doped tin oxide (FTO) substrate under
atmosphere. It is a highly challenging task to make a uniform
coverage of the perovskite film on FTO using spin coating in an
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ambient atmosphere. Accordingly, we optimized the parameters,


such as concentration of both methylammonium iodide (MAI)
and lead iodide (PbI2) spin speed with respect to the number of Fig. 1 X-ray diraction spectra of the MAPbI3 perovskite film (a) at RT and
layers deposited, and annealing time and temperature, and those annealed at 60 1C, 100 1C, and 150 1C for 10 minutes, and (b) those
annealed at 60 1C for 10, 30, 60 and 120 minutes.
utilized dierent solvents based on their dielectric constant
to help us to achieve uniform film coverage with stability.
Subsequently, the samples were employed in dierent physical were corrected using the fixed core level peak of adventitious
characterization techniques to examine the quality of the film carbon (C 1s) at 284.6 eV as a reference. We used the lowest
through structural and morphological properties. The phase possible number of components to fit the data satisfactorily.
transition occurs at 60 1C for the films annealed for 30 minutes The uncertainty in the binding energy position was within
and the noticeable changes in the binding states according to 0.05 eV for a particular component. Peak fitting and quantitative
atmospheric eects are discussed in this work. analysis were done using the Casa XPS program (Casa Software
Ltd) and the results were justified using an average matrix
relative sensitivity factor (AM-RSF) with respect to the peak area
2. Experimental and atomic sensitivity factor of the identified components. The
2.1 Preparation of the MAPbI3 thin film binding energy of the identified components was assigned
from the NIST X-ray Photoelectron Spectroscopy Database (NIST
The FTO substrates (710 O cm1, Hartford Glass Corporation)
Standard Reference Database 20, Version 4.1).
were well-cleaned in an ultrasonic bath with ethanol, acetone
and deionized water sequentially for 10 minutes each followed
by drying under N2 gas. All chemicals were purchased from
Sigma Aldrich and used as received unless otherwise stated. 3. Results and discussion
The MAPbI3 perovskite precursor was prepared by dissolving a 3.1 Structural analysis
2 : 1 molar ratio of MAI and PbI2 in N,N-dimethylformamide XRD analysis was carried out to understand the eect of
(DMF) and stirring at 60 1C overnight. The MAPbI3 precursor temperature on the structural properties of the MAPbI3 films
solution was drop cast on FTO for three consecutive cycles at an processed in atmospheric conditions. Fig. 1(a) shows the XRD
optimized spin speed of 2000 rpm for 30 s. After spin coating, for the MAPbI3 films annealed at 60 1C, 100 1C and 150 1C for
each set of films was annealed at 60 1C, 100 1C or 150 1C in air 10 minutes. The diraction peaks of FTO at 26.52, 33.67, and
for 10, 30, 60 or 120 minutes. 37.751 are assigned to the (222), (314) and (200) lattice planes,
respectively. The MAPbI3 thin films have a preferential orienta-
2.2 Characterization tion with a = 8.789 and c = 12.567 axes for a tetragonal
The phase identification of the spin-coated MAPbI3 perovskite perovskite structure at RT with the (110), (202), (220), (310),
films were analysed using X-ray diraction (XRD; Bruker D8- (224), (314) and (330) lattice planes corresponding to the 14.10,
Advance) with a Cu Ka radiation (l = 1.540 ) source operated at 24.5, 28.50, 31.87, 40.55, 43.17 and 44.601 (2y) diraction positions,
40 kV and 30 mA in the range of 10601. UV-visible spectroscopy respectively.15,16 The indexing was performed by the relative combi-
was performed using an Optizen 3220 UV spectrophotometer in nation of planar-spacing and Braggs law, which determined
the 400800 nm wavelength range. The morphology of the films the unit cell parameters from the peak positions.17,18 The
was observed using a field-emission scanning electron micro- intensity of the MAPbI3 characteristic peaks gradually increased
scopy (FE-SEM) (Hitachi, model S-4200) operated at 15 kV, with decreasing full width at half maximum when the annealing
150 W. X-ray photoelectron spectroscopy (XPS) was performed temperature was increased, along with few peaks disappearing
using a Thermo Fisher Scientific (UK) ESCALAB 250 system and new minor peaks appearing at 150 1C due to the elimination
with monochromatic Al Ka radiation at 1486.6 eV and with an of defects. The substantial changes in the MAPbI3 perovskite
electron take off angle of 451. The measurement was conducted crystal structure from tetragonal to cubic occurs at 60 1C through
without ion etching, to avoid reconfiguration of the bonds. The unit cell distortion and this crystal structure is maintained
pressure of the chamber was kept at 1010 Torr during the even at 150 1C with increased grain size. Fig. 1(b) shows XRD
measurement. The survey spectrum was scanned in the binding spectra of MAPbI3 thin films annealed at 60 1C for 30, 60 and
energy (BE) range of 1001200 eV in scan steps of 1 eV with a 120 minutes. Even though, the crystal growth has been initiated
spot size of 500 mm. All of the obtained binding energy values at RT itself, the film structure is significantly reformed at 60 1C

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Fig. 2 XRD spectra of the MAPbI3 thin films annealed at 60 1C for (a)
10 minutes (tetragonal), and (b) 30 minutes (cubic). Inset shows the
splitting of diraction peaks.
Fig. 4 Graphical images of the structural transformation of the MAPbI3
perovskite from tetragonal to cubic phase.

annealed for 30 minutes. It is observed that the shifting of


MAPbI3 characteristic peaks occurs towards the lower angles and the atomic disordering of iodide (I) ions, which may
and new peaks appear for the (111), (112), (004), (312) and (324) decrease or increase its symmetry in the way of expansion or
lattice planes corresponding to the 19.59, 20.85, 28.80, 46.24, contraction.20,21
46.751 (2y) positions, respectively. The diraction peak of (220) The tetragonal symmetry has been distorted only along one
that splits into the (004) and (220) crystal planes for the films preferential axis, which changes the unit cell dimensions and
annealed at 60 1C for 30 minutes indicates the structural generates more diraction lines as well as shifts in its peak
transformation of MAPbI3 from the tetragonal to the cubic positions. The average grain sizes were calculated using Scherrers
crystal structure19 and is shown in Fig. 2. However, there is formula (eqn (A) in the ESI)2224 and are 36.0, 39, 47.7, and 59.1 nm
no significant change in the crystal structure observed even for the films annealed at 60 1C for 10, 30, 60 and 120 minutes,
when the annealing time is increased up to 120 minutes at respectively.
60 1C. Parallel results are obtained for higher annealing tem-
peratures of 100 1C and 150 1C, as is shown in Fig. 3. The phase 3.2 Optical and morphological studies
transformation of the perovskite from tetragonal to cubic is UV-visible spectroscopy studies were carried out to investigate
schematically represented in Fig. 4. The transformed phase is the thermal eects on the electronic band gap of MAPbI3 thin
highly conserved at the longer annealing time of 120 minutes films. Fig. 5(a) shows the absorption spectra of the MAPbI3 thin
and higher annealing temperature of 150 1C. The phase transi- films annealed for 10 minutes at dierent temperatures. The
tion of perovskite is mainly due to its low tolerance factor of exciton state in the organicinorganic interface of MAPbI3 is
0.83 and the alteration of the d spacing upon annealing.8 The mainly associated with the bandgap of the inorganic layers
tetragonal crystal structure exhibited below 60 1C is distorted by which deliver a sharp peak even at RT.25,26 The absorption
the thermal vibration of the lattice planes upon annealing by spectra exhibits a very wide spectral response over the entire
the rotational disorder of MA+ ions due to the short relaxation visible range, the exciton peak appears in the range of
400450 nm and onset of absorption is between 700 and
800 nm. Fig. 5(b) shows the absorption spectra of films
annealed at 60 1C for 10, 30, 60 and 120 minutes to further
examine the variation of the band gap. Fig. S1 (ESI) shows the
UV-Visible spectra of MAPbI3 perovskite annealed at 100 1C and
150 1C for 1 and 2 hours and shows very little influence on
absorption and band gap energy. It is observed that the
absorption onset shifts towards the longer wavelength region
with increased annealing temperature and time. The reduced
optical bandgap energy with respect to annealing temperature
and time is because of the increased grain size.27,28 The band
gaps of the MAPbI3 films were estimated using the absorption
spectrum fitting (ASF) method,29,30 where the absorption
coefficient as a function of wavelength (l) is
 
m1 1 1 m
al Bhc l  : (1)
l lg

Here, lg, c, and h are the wavelength corresponding to the


Fig. 3 XRD spectra of the MAPbI3 thin films annealed at 100 1C and 150 1C optical bandgap, the velocity of light and Plancks constant,
for 60 and 120 minutes. respectively.

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Fig. 6 ASF plots for the MAPbI3 thin film at (a) RT and those annealed at (b)
60 1C, (c) 100 1C, and (d) 150 1C for 10 minutes.

for 1 and 2 hours have minor changes in their bandgaps of


1.55, 1.53, 1.52, and 1.51 eV, respectively. Upon annealing, the
bandgap may also decrease due to the thermal vibrations of
the organic (MA+) crystal ions that weakly interact with the
inorganic species (Pb) via intermolecular hydrogen bonding
occurring through the NH3+ group, which predominantly reduces
the surface energy of organicinorganic interfaces.32,33 It is also
suggested that a longer annealing time increases the grain size
by the agglomeration of grains at the surface of the film, as
Fig. 5 UV-Vis absorption spectra of the MAPbI3 thin film at (a) RT and confirmed in the XRD and morphological analysis.
those annealed at 60 1C, 100 1C, and 150 1C for 10 minutes, and (b) after
The SEM images (Fig. 7(ad)) depict the thermal effects on the
annealing at 60 1C for 10, 30, 60 and 120 minutes.
surface morphology of the MAPbI3 perovskite at RT and those
annealed at 60 1C, 100 1C and 150 1C for 10 minutes under ambient
Using BeerLamberts law in eqn (1): atmosphere. Instantly after spin coating, the film is covered
  with quite a high number of pinholes, as shown in Fig. 7(a).
1 1 m
Absl B1 l  B2 : (2) Upon annealing at 60 1C, the number of pinholes have reduced
l lg
that stimulate the formation of tightly packed agglomerated
  grains at the surface until the crystallization is completed at the
d
Here B1 Bhcm1  and B2 are constants. bottom layer of MAPbI3 perovskite. If the annealing tempera-
2:303
Eqn (2) was used to estimate the bandgap using the ASF ture is increased to 100 1C, the size of the grains increases with
method without the need of the film thickness. The value of the voids in between due to the agglomeration of small islands
band gap in eV can be calculated from the parameter lg using to become larger crystallites, as is shown in Fig. 7(c). The
  formation of still larger crystallites associated with the voids
ASF 1239:83 in between is observed at 150 1C (Fig. 7(d)). The change in
Egap : (3)
lg surface morphology due to annealing is mainly caused by the
excess surface energy gained from the lattice which tends to
The lg value can be calculated from Fig. 6(ad) by extrapolating
increase the rate of perovskite crystallization at the organic
 1    1
A m 1 A m inorganic interfaces of MAPbI3 in air.34
the linear region of vs: curve at 0: Here, m is
l l l Fig. 7(e and f) illustrate the morphological transformation of
the index that depends on the nature of the optical transition. the MAPbI3 perovskite from agglomerated crystals (Fig. 7e) to
For direct band gap materials m = 1/2 and m = 2 for indirect densely arranged needle like crystals. It is suggested that the
band gap materials.31 change in annealing time facilitates the surface tension to
Fig. 6 shows the band gap energies for the film prepared at RT upsurge the rate of perovskite crystallization by stretching the
and those annealed at 60 1C, 100 1C, and 150 1C for 10 minutes bonds at the surface of the MAPbI3 film.35,36 This extended
and they are 1.73, 1.66, 1.62, and 1.56 eV, respectively. Fig. S1 surface energy may be minimized if the atoms have enough
(ESI) shows the perovskite films annealed at 100 1C and 150 1C energy and time to diuse to lower energy nucleation sites.37,38 At

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Fig. 7 SEM images of the MAPbI3 film at (a) RT and those annealed at
(b) 60 1C, (c) 100 1C, and (d) 150 1C for 10 minutes and (e) 60 1C for
30 minutes. (f) A higher magnification image of (e).

lower annealing temperatures, large numbers of critical nuclea-


tion sites are formed that tend to form smaller crystallites and
higher annealing temperatures result in fewer nucleation sites,
causing the formation of larger crystallites at the surface.

3.3 Surface analysis of the MAPbI3 perovskites


The XPS spectra were recorded to investigate the interaction of
organicinorganic species in the MAPbI3 thin films and to
understand the impact of annealing on the elemental chemical
states and relative surface elemental composition. The XPS
survey spectra are shown in Fig. S2 (ESI). The small features
at binding energies of 284.7, 401.0 and 531.0 eV correspond to
the photoelectron peaks of C 1s, N 1s, and O 1s, respectively.
The doublet peaks of I and Pb are located at 618 and 137 eV,
respectively, with spin orbit splitting.39 The elemental surface
composition of MAPbI3 is depicted in Fig. S2 (ESI).
3.3.1 High resolution X-ray photoelectron (HRXPS) spectra Fig. 8 XPS core-level spectra of (ad) C 1s, (eh) O 1s, and (il) N 1s for
of the MAPbI3 thin films. High resolution XPS spectra were the MAPbI3 thin films at RT and annealed at 60 1C, 100 1C, and 150 1C for
acquired over much restricted ranges to evaluate the thermal 10 minutes in air.
eects on the dierent chemical states of the same element and
the atomic concentration. Typically, the atomic concentration
of the element was extracted from the core-level spectra using the spectra of C 1s, O 1s, and N 1s for the MAPbI3 perovskite
CASA XPS software with the average matrix relative sensitivity factors at RT and the films annealed at 60 1C, 100 1C, and 150 1C for
(AM-RSFs)40,41 according to eqn (B), given in the ESI (Fig. S3, ESI). 10 minutes are shown in Fig. 8(al). The deconvoluted char-
The XPS data were fitted with GaussianLorentzian (30% Gaussian) acteristics of the carbon peaks exhibited the bound state of the
functions and a Shirley type background.42 The core-level carbon species with atmospheric oxygen, shown in Fig. 8(ad).

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O and carbonyl (CQO) species at 150 1C leads to the appear-


ance OCQO and OQCN species at the higher binding
energies of 534.64 and 535.42 eV, respectively. Fig. 8(il) shows
the XPS N 1s core level spectra of the MAPbI3 film at RT and
films annealed at 60 1C, 100 1C, and 150 1C for 10 minutes.
At RT, the N 1s spectrum is deconvoluted to three spectral
contributions such as single and double bonded nitrogen
atoms with carbon atoms (NC, NQC) and amide ions (NH2)
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located at the binding energies 398.70, 398.92, and 399.31 eV,


respectively.45 The appearance of an amide group (NCQO) is
thermodynamically favourable at 100 1C and 150 1C.
The doublet orbitals of Pb (4f7/2 and 4f5/2) and I (3d3/2 and
3d5/2) are quantified with an area ratio of 3 : 4 and 2 : 3 and
elemental spin orbit splitting (SOS) of 11.5 and 4.8, respectively,
was fixed with an equal FWHM.
Prior to the peak fitting of Pb and I, the transition intensity
is measured using two independent quantification regions to
avoid the creation of a poor background with high residues.
Fig. 9(ad) show the deconvoluted XPS spectra of the I 3d
doublets of 3d5/2 at 619.5 and 631 eV, corresponding to the
I3 charge state, and 3d3/2 at 619.37 and 630.87, corresponding
to the I2+ charge state. Fig. 9(eh) show the Pb core-level
doublet spectra of 4f7/2 at 138.0 and 142.8 eV, corresponding
to metallic lead (Pb), and the 4f5/2 peaks at 137.7 and 142.5 eV
correspond to Pb(II).46 The significant change in the surface
states of the Pb 4f core levels indicates the surface re-structuring
of the Pb atoms into Pb ions with oxygen states upon annealing.
Particularly, the Pb(II) species percentage is relatively higher than
the metallic Pb, even while increasing the temperature up to
150 1C, which illustrates that the iodine species strongly interact
with the Pb species and form donoracceptor complexes (PbI
Fig. 9 XPS core level spectra of the (ad) I 3d and (eh) Pb 4f doublets for
charge transfer interface) between the iodine atoms and Pb
the MAPbI3 thin film at RT and the films annealed at 60 1C, 100 1C and
150 1C for 10 minutes. atoms.47 The internal charge transfer occurs between the valence
states of Pb and iodine (I) atoms such as the low electronegative
(Pauling scale 1.87) Pb atom donates its excess unpaired elec-
At RT, the peak at 283.17 eV is assigned to the aliphatic trons (outermost p subshells) to the highly electronegative
hydrocarbon (CH/CC) and the peak at 283.97 eV corresponds (Pauling scale 2.66) iodine (I). During the electron transfer
to the hydroxyls (COH). The next higher binding energy peak at process, the Pb gets oxidized to attain its oxidation state 2+ as
284.84 eV corresponds to the carbon atoms bonded to single a Pb2+ ion and iodine is reduced to an iodide ion (2I). The
nitrogen atoms (CN). The carbon adjacent to (CQO) is the most remaining unpaired electrons in the 4f valence levels (outermost
electron withdrawing environment and corresponds to the peak at s subshells) of the Pb atoms have either parallel or anti-parallel
285.81.43 This distortion causes the variation of atomic concen- orientation to the orbital angular momentum that causes the
tration of the C 1s components and is given in Fig. 8(ad). energy difference in the Pb 4f valence states.
The hygroscopic nature of the MAPbI3 thin films was sub- Fig. 10(ac) shows the HRXPS spectra of C 1s, O 1s, and the
jected to surface oxidation when exposed to air. Fig. 8(eh) N 1s singlet for the MAPbI3 perovskite annealed at 60 1C for
show the O 1s core level spectra deconvoluted into five oxygen 30 minutes. The estimation of binding states with atomic
binding states located at 530.51, 531.17, 532.06, 532.16 and concentration is a significant aspect of revealing the thermal
533.22 eV that come from weakly adsorbed O molecules from effects on the MAPbI3 perovskite in the XPS spectra. In
air, hydroxyls (COH), carbonyls (CQO), (CO) and aliphatic Fig. 10(a) the C 1s core-level spectra of the 30 minute annealed
OCO, respectively, for the film at RT and those annealed at at 60 1C film exhibited additional binding states due to the
60 1C, 100 1C, and 150 1C. It is found that MAPbI3 films presence of epoxy carbons (COC) and carboxylate carbons
are drastically affected by surface oxidation resulting from (OCQO) at 288.03 and 289.33 eV, respectively, compared to
chemisorbed or dissociated oxygen species. It is clear that the the 10 minute annealed film (Fig. 8(b)).46 The increase in the
variation in the atomic percentage of O 1s is mainly attributed annealing time could incorporate additional oxygen free radicals
to the elimination of weakly bonded organic components at to the carbon species that would shift the binding energy
higher annealing temperature.44 The reduction of chemisorbed positions. Moreover, Fig. 10(b) shows the O 1s spectra with

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Fig. 11 HRXPS core level spectra of (a) I 3d and (b) Pb 4f for the MAPbI3
thin film annealed at 60 1C for 30 minutes.

increase in annealing time might have led to the delocalization


of the halide free radicals that directly bond to the surface
oxygen atoms.48 The noticeable shift in the O 1s maxima could
be due to the incorporation of additional oxygen atoms into the
distorted lattice of the metalhalide complex. On the other hand,
the N 1s core level spectra (Fig. 10(c)) exhibited distinguished
binding states of an amide carbonyl (NCQO) at 398.60 eV, and
nitrogen singly bonded with oxygen atoms (NH) at 397.24 eV
might be arising from dehydrogenated NH2 binding states.46
The core-level 4f spectrum of Pb for the MAPBI3 films
annealed at 60 1C for 30 minutes is shown in Fig. 11(b) with
Fig. 10 Core-level spectra of (a) C 1s, (b) O 1s, and (c) N 1s for the MAPbI3 an additional two doublets associated with metallic lead (Pb(0))
thin film annealed at 60 1C for 30 minutes.
at 137.77 and 142.65 eV and oxidised lead(II) at 138.20 and
143.08 eV.46 The unsaturated Pb reveals the metallic character-
additional peaks due to lattice oxygen (O2), iodate (IO3) and istics of lead and indicates a deficiency of iodide species in the
carboxylates (OCQO) at binding energies of 528.44, 529.95 and perovskite lattice; the metallic lead species in the 10 minute
534.76 eV, respectively. It is suggested that the hygroscopic annealed film could act as recombination centres.49 The increase
methylammonium cation could have more strongly bonded in the annealing time further oxidizes the Pb 4f species and is
with the oxygen than the metalhalide (PbI) complex under confirmed by the existence of lead monoxide (PbO) at 144.25 eV
atmospheric conditions in the 10 minute annealed films. In (1.69%) and 137.05 eV (3.32%).
addition, the ionic radius of the organic cation is much larger The high resolution XPS spectra of I 3d (annealed at 60 1C
than those of the inorganic lead and halide ions and hence, an for 30 min) is shown in Fig. 11(a). Iodine exhibits a very strong

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