Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties

作者：Constantinos C. Stoumpos, Christos D. Malliakas, Mercouri G. Kanatzidis · 发表于：Inorganic Chemistry · 年份：2013 · DOI：10.1021/ic401215x · 被引用次数：5433 · 研究领域：Perovskite Materials and Applications、Solid-state spectroscopy and crystallography、Luminescence Properties of Advanced Materials

A broad organic-inorganic series of hybrid metal iodide perovskites with the general formulation AMI3, where A is the methylammonium (CH3NH3(+)) or formamidinium (HC(NH2)2(+)) cation and M is Sn (1 and 2) or Pb (3 and 4) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of 1-4 classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100-400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a strong dependence of the resistivity as a function of the crystal structure. Optical absorption measurements indicate that 1-4 behave as direct-gap semiconductors with energy band gaps distributed in the range of 1.25-1.75 eV. The compounds exhibit an intense near-IR photoluminescence (PL) emission in the 700-1000 nm range (1.1-1.7 eV) at room temperature. We show that solid solutions between the Sn and Pb compounds are readily accessible throughout the composition range....