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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.
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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.
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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.
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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).
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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.
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interaction with atmospheric oxygen since the doublets of 3d5/2 4 I. J. Kramer and E. H. Sargent, Chem. Rev., 2013, 114,
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valence states corresponding to iodide (I) at 629.33 and 5 G. Li, R. Zhu and Y. Yang, Nat. Photonics, 2012, 6, 153161.
617.83 eV, triiodide (I3) at 619.01 and 630.49 eV, and iodite 6 J. A. Chang, J. H. Rhee, S. H. Im, Y. H. Lee, H.-j. Kim,
(IO2) at 620.20 and 631.81 eV, respectively. The increase in S. I. Seok, M. K. Nazeeruddin and M. Gratzel, Nano Lett.,
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lead to the formation of the iodite (IO2) anion and the I2+ 7 N.-G. Park, J. Phys. Chem. Lett., 2013, 4, 24232429.
cation, easily reduced to the iodide (I) anion (oxidation state of 8 M. A. Green, A. Ho-Baillie and H. J. Snaith, Nat. Photonics,
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