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Article

Tuning the Band Gap in Hybrid Tin Iodide Perovskite Semiconductors Using Structural Templating

Jeremy L. Knutson and James D. Martin*

Department of Chemistry, North Carolina State University, Box 8204, Raleigh, North Carolina 27695

David B. Mitzi

IBM T. J. Watson Research Center, P.O. Box 218, Yorktown Heights, New York 10598

Inorg. Chem., 2005, 44 (13), pp 4699–4705

DOI: 10.1021/ic050244q

Publication Date (Web): May 25, 2005

To whom correspondence should be addressed. E-mail: JDMARTIN@ NCSU.EDU.

Abstract

Structural distortions within the extensive family of organic/inorganic hybrid tin iodide perovskite semiconductors are correlated with their experimental exciton energies and calculated band gaps. The extent of the in- and out-of-plane angular distortion of the SnI₄²^- perovskite sheets is largely determined by the relative charge density and steric requirements of the organic cations. Variation of the in-plane Sn−I−Sn bond angle was demonstrated to have the greatest impact on the tuning of the band gap, and the equatorial Sn−I bond distances have a significant secondary influence. Extended Hückel tight-binding band calculations are employed to decipher the crystal orbital origins of the structural effects that fine-tune the band structure. The calculations suggest that it may be possible to tune the band gap by as much as 1 eV using the templating influence of the organic cation.

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Published In Issue June 27, 2005
Received February 16, 2005

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Article

Tuning the Band Gap in Hybrid Tin Iodide Perovskite Semiconductors Using Structural Templating