Journal of Materials Science

, Volume 53, Issue 1, pp 356–368 | Cite as

Investigation of earth-alkaline (EA = Mg, Ca, Sr) containing methylammonium tin iodide perovskite systems

  • Lucangelo DimessoEmail author
  • Chittaranjan Das
  • Thomas Mayer
  • Wolfram Jaegermann


Methylammonium tin iodide systems containing earth-alkaline ions (CH3NH3Sn1−x (EA) x I3, EA = Ca2+, Sr2+, Mg2+, 0 ≤ x ≤ 0.30) were investigated. The X-ray diffraction patterns detected the formation of tetragonal nearly cubic CH3NH3SnI3 (space group P4mm), SnI2, and not identified phases. The morphological analysis confirmed the presence of secondary phases with formation of irregularly shaped crystallites. The Sn3d and I3d photoemission spectra revealed the typical position and separation of spin–orbit components for Sn2+ in halides. Static thermogravimetric measurements (T = 85 °C) showed a barely measurable weight loss for EA = Mg, a dramatic decrease of the weight loss rate for EA = Ca, and recorded weight losses till t ≈ 1.5 h only for EA = Sr, respectively. The optical spectra displayed absorption edges which increased at increasing the (EA)-content with maximum values for x = 0.050 (λ on-set = 1754 nm, EA = Mg; λ on-set = 1692 nm, EA = Ca; and λ on-set = 1338 nm, EA = Sr, respectively). The Tauc plots revealed a direct semiconducting behavior with band energy gaps depending on the nature and amount of the (EA)-ions. The photoluminescence (PL) spectra showed, for EA = Mg, an increase of the PL-band intensity at increasing the Mg content with a maximum at x = 1.0 and, for EA = Ca, an increase of band intensity at increasing the Ca-content and for EA = Sr, a band intensity maximum at x = 0.025. This was explained by the similar ionic radius between Sn2+ and Sr2+ ions which can be easily exchanged in the SnI6 2− octahedra.



Many thanks are owed to Mr. J.C. Jaud for technical assistance in XRD analysis and to Mrs. C. Fasel for the technical assistance in the dynamic and static thermal analysis. The authors thank the Federal Ministry of Research and Development (BMBF) (Project “Perosol” No. 03SF0483B) for the financial support during this work.

Compliance with ethical standards

Conflicts of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2017_1545_MOESM1_ESM.tif (4.9 mb)
Figure S1 XRD patterns of CH3NH3Sn1−x(EA)xI3 systems (0.0 ≤ x ≤ 0.3) for A) EA = Mg; B) EA = Ca; and C) EA = Sr, respectively. “P” indicates the nearly cubic perovskite phase (P4mm space group) (TIFF 5017 kb)
10853_2017_1545_MOESM2_ESM.tif (3.1 mb)
Figure S2 O1 s photoelectron emission spectra of the CH3NH3Sn0.95(EA)0.05I3 systems (TIFF 3169 kb)


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© Springer Science+Business Media, LLC 2017

Authors and Affiliations

  1. 1.Materials Science DepartmentTechnische Universitaet DarmstadtDarmstadtGermany

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