Structural phase transition causing anomalous photoluminescence behavior in perovskite (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}]

Journal Article · Mon Dec 14 00:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4936776· OSTI ID:22493310

Yangui, A. ^[1]; Pillet, S. ^[2]; Mlayah, A. ^[3]; Lusson, A.; Bouchez, G.; Triki, S. ^[4]

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1. Groupe d’Etudes de la Matière Condensée, UMR CNRS 8653-Université de Versailles Saint Quentin En Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles (France)
2. Laboratoire de Cristallographie, Résonance Magnétique et Modélisations, UMR-CNRS 7036, Institut Jean Barriol, Université de Lorraine, BP 239, 54506 Vandoeuvre-lès-Nancy (France)
3. Centre d’Elaboration de Matériaux et d’Etudes Structurales (CEMES), CNRS UPR 8011-Université de Toulouse, 29 rue Jeanne Marvig 31055, Toulouse, Cedex 4 (France)
4. Laboratoire de Chimie, Electrochimie Moléculaires, Chimie Analytique, UMR CNRS 6521-Université de Bretagne Occidentale, BP 809, 29285 Brest (France)

Optical and structural properties of the organic-inorganic hybrid perovskite-type (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}] (abbreviated as C{sub 6}PbI{sub 4}) were investigated using optical absorption, photoluminescence (PL), and x-ray diffraction measurements. Room temperature, optical absorption measurements, performed on spin-coated films of C{sub 6}PbI{sub 4}, revealed two absorption bands at 2.44 and 3.21 eV. Upon 325 nm (3.815 eV) laser irradiation, strong green PL emission peaks were observed at 2.41 eV (P1) and 2.24 eV (P2) and assigned to free and localized excitons, respectively. The exciton binding energy was estimated at 356 meV. At low temperature, two additional emission bands were detected at 2.366 eV (P3) and a large band (LB) at 1.97 eV. The former appeared only below 40 K and the latter emerged below 130 K. The thermal dependence of the PL spectra revealed an abnormal behavior accompanied by singularities in the peak positions and intensities at 40 and 130 K. X-ray diffraction studies performed on powder and single crystals as a function of temperature evidenced significant changes of the interlayer spacing at 50 K and ∼138 K. Around 138 K, a commensurate to incommensurate structural phase transition occurred on cooling. It involves a symmetry breaking leading to a distortion of the PbI{sub 6} octahedron. The resulting incommensurate spatial modulation of the Pb–I distances (and Pb–I–Pb angles) causes a spatial modulation of the band gap, which is at the origin of the emergence of the LB below ∼130 K and the anomalous behavior of the position of P1 below 130 K. The change of the interlayer spacing in the 40-50 K range may in turn be related to the significant decrease of the intensity of P2 and the maximum emission of the LB. These results underline the intricate character of the structural and the PL properties of the hybrid perovskites; understanding such properties should benefit to the design of optoelectronic devices with targeted properties.

• OSTI ID: 22493310
• Journal Information: Journal of Chemical Physics, Vol. 143, Issue 22; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM COMPOUNDS
BINDING ENERGY
EV RANGE
EXCITONS
HYBRIDIZATION
HYDROCARBONS
LASER RADIATION
LEAD IODIDES
MODULATION
MONOCRYSTALS
OPTOELECTRONIC DEVICES
PEROVSKITE
PHASE TRANSFORMATIONS
PHOTOLUMINESCENCE
POWDERS
SPIN
SYMMETRY BREAKING
TEMPERATURE DEPENDENCE
X-RAY DIFFRACTION