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Title: Evidence and detailed study of a second-order phase transition in the (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}] organic-inorganic hybrid material

The thermal properties of the organic-inorganic hybrid material (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}] are investigated using diffuse reflectivity, spectroscopic ellipsometry, differential scanning calorimetry, Raman spectroscopy, and X-ray diffraction. The diffuse reflectivity, performed in heating mode, clearly evidences the presence of a singularity at 336 K. This is confirmed by the temperature dependence of the spectroscopic ellipsometry spectra, which points out a second-order phase transition at 336 K with a critical exponent ∼0.5. Differential scanning calorimetry measurements on a polycrystalline powder of (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}] show a reversible phase transition detected at T{sub C} = 336 K without hysteresis. Raman spectroscopy data suggest that this transition arises from a change in the interactions between inorganic sheets (([PbI{sub 4}]{sup 2−}){sub ∞}) and organic protonated molecules ([C{sub 6}H{sub 11}NH{sub 3}]{sup +}). The structural analysis from power X-ray diffraction reveals an incomplete order-disorder transition of the cyclohexylammonium cation, causing a subtle contraction of the inter-plane distance. The transition results from repulsive close contacts between the organic molecules in the interlayer spacing.
Authors:
 [1] ;  [2] ;  [3] ; ;  [1] ;  [4] ;  [5]
  1. Groupe d'Etudes de la Matière Condensée, CNRS-Université de Versailles Saint Quentin En Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles (France)
  2. (Tunisia)
  3. Laboratoire de Cristallographie, Résonance Magnétique et Modélisations, UMR-CNRS 7036, Institut Jean Barriol, Université de Lorraine, BP 239, 54506 Vandoeuvre-lès-Nancy (France)
  4. UMR CNRS 6521, Chimie, Electrochimie Moléculaires, Chimie Analytique, Université de Bretagne Occidentale, BP 809, 29285 Brest (France)
  5. Laboratoire de Physique Appliquée, Faculté des Sciences de Sfax, Route de Soukra km 3.5 BP 1171, 3018 Sfax (Tunisia)
Publication Date:
OSTI Identifier:
22399323
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Applied Physics; Journal Volume: 117; Journal Issue: 11; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CALORIMETRY; CATIONS; DIFFERENTIAL THERMAL ANALYSIS; ELLIPSOMETRY; HYSTERESIS; LEAD IODIDES; MOLECULES; ORDER-DISORDER TRANSFORMATIONS; POLYCRYSTALS; POWDERS; RAMAN SPECTROSCOPY; REFLECTIVITY; SPECTRAL REFLECTANCE; TEMPERATURE DEPENDENCE; THERMODYNAMIC PROPERTIES; X-RAY DIFFRACTION