Ferroelectricity of CH3NH3PbI3 Perovskite.

Ferroelectricity has been believed to be an important but controversial origin of the excellent photovoltaic performance of organometal trihalide perovskites (OTPs). Here we investigate the ferroelectricity of a prototype OTP, CH3NH3PbI3 (MAPbI3), both theoretically and experimentally. Our first-principles calculations based on 3-D periodic boundary conditions reveal that a ferroelectric structure with polarization of ∼8 μC/cm(2) is the globally stable one among all possible tetragonal structures; however, experimentally no room-temperature ferroelectricity is observed by using polarization-electric field hysteresis measurements and piezoresponse force microscopy. The discrepancy between our theoretical and experimental results is attributed to the dynamic orientational disorder of MA(+) groups and the semiconducting nature of MAPbI3 at room temperature. Therefore, we conclude that MAPbI3 is not ferroelectric at room temperature; however, it is possible to induce and experimentally observe apparent ferroelectric behavior through our proposed ways. Our results clarify the controversy of the ferroelectricity in MAPbI3 and also provide valuable guidance for future studies on this active topic.

[1]  Aron Walsh,et al.  Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells , 2014, 1405.5810.

[2]  Nakita K. Noel,et al.  Anomalous Hysteresis in Perovskite Solar Cells. , 2014, The journal of physical chemistry letters.

[3]  Jean-Marc Triscone,et al.  Physics of ferroelectrics : a modern perspective , 2007 .

[4]  U. V. Waghmare,et al.  First-principles study of spontaneous polarization in multiferroic BiFeO 3 , 2005 .

[5]  Fan Zheng,et al.  First-Principles Calculation of the Bulk Photovoltaic Effect in CH3NH3PbI3 and CH3NH3PbI(3-x)Cl(x). , 2015, The journal of physical chemistry letters.

[6]  K. P. Ong,et al.  Mechanical Origin of the Structural Phase Transition in Methylammonium Lead Iodide CH3NH3PbI3. , 2015, The journal of physical chemistry letters.

[7]  Laura M Herz,et al.  High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites , 2013, Advanced materials.

[8]  Aron Walsh,et al.  Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells , 2014, Nano letters.

[9]  G. Scuseria,et al.  Restoring the density-gradient expansion for exchange in solids and surfaces. , 2007, Physical review letters.

[10]  Peng Gao,et al.  Impedance spectroscopic analysis of lead iodide perovskite-sensitized solid-state solar cells. , 2014, ACS nano.

[11]  Furkan H. Isikgor,et al.  Efficiency enhancement of planar perovskite solar cells by adding zwitterion/LiF double interlayers for electron collection. , 2015, Nanoscale.

[12]  Albrecht Poglitsch,et al.  Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy , 1987 .

[13]  H. Mashiyama,et al.  Structural Study on Cubic–Tetragonal Transition of CH3NH3PbI3 , 2002 .

[14]  Stephen Jesse,et al.  The role of electrochemical phenomena in scanning probe microscopy of ferroelectric thin films. , 2011, ACS nano.

[15]  Yongbo Yuan,et al.  Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells , 2014, Nature Communications.

[16]  W. Geng,et al.  First-Principles Study of Lead Iodide Perovskite Tetragonal and Orthorhombic Phases for Photovoltaics , 2014 .

[17]  Ronald E. Cohen,et al.  Polarization rotation mechanism for ultrahigh electromechanical response in single-crystal piezoelectrics , 2000, Nature.

[18]  K. P. Ong,et al.  Stable ferroelectric perovskite structure with giant axial ratio and polarization in epitaxial BiFe0.6Ga0.4O3 thin films. , 2015, ACS applied materials & interfaces.

[19]  Yuanyuan Zhou,et al.  Direct Observation of Ferroelectric Domains in Solution-Processed CH3NH3PbI3 Perovskite Thin Films. , 2014, The journal of physical chemistry letters.

[20]  David Cahen,et al.  Elucidating the charge carrier separation and working mechanism of CH3NH3PbI3−xClx perovskite solar cells , 2014, Nature Communications.

[21]  D. Vanderbilt,et al.  Theory of polarization of crystalline solids. , 1993, Physical review. B, Condensed matter.

[22]  Tsutomu Miyasaka,et al.  Emergence of Hysteresis and Transient Ferroelectric Response in Organo-Lead Halide Perovskite Solar Cells. , 2015, The journal of physical chemistry letters.

[23]  Fan Zheng,et al.  Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites. , 2015, The journal of physical chemistry letters.

[24]  Yongli Gao,et al.  Qualifying composition dependent p and n self-doping in CH3NH3PbI3 , 2014 .

[25]  Mercouri G Kanatzidis,et al.  Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. , 2013, Inorganic chemistry.

[26]  Eric T. Hoke,et al.  Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells , 2014 .

[27]  Fujun Zhang,et al.  Anomalously large interface charge in polarity-switchable photovoltaic devices: an indication of mobile ions in organic–inorganic halide perovskites , 2015 .

[28]  Paolo Umari,et al.  Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications , 2014, Scientific Reports.

[29]  Qingfeng Dong,et al.  Giant switchable photovoltaic effect in organometal trihalide perovskite devices. , 2015, Nature materials.

[30]  Heng Li,et al.  Hysteresis Analysis Based on the Ferroelectric Effect in Hybrid Perovskite Solar Cells. , 2014, The journal of physical chemistry letters.

[31]  Hiroyuki Hasegawa,et al.  Hall mobility in tin iodide perovskite CH{sub 3}NH{sub 3}SnI{sub 3}: Evidence for a doped semiconductor , 2013 .

[32]  M. Grätzel,et al.  Title: Long-Range Balanced Electron and Hole Transport Lengths in Organic-Inorganic CH3NH3PbI3 , 2017 .

[33]  Young Chan Kim,et al.  Compositional engineering of perovskite materials for high-performance solar cells , 2015, Nature.

[34]  Martin Schreyer,et al.  Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3) PbI3 for solid-state sensitised solar cell applications , 2013 .

[35]  A. Baldereschi,et al.  Towards a quantum theory of polarization in ferroelectrics: The case of KNbO3. , 1993, Physical review letters.

[36]  D. Vanderbilt,et al.  Electric polarization as a bulk quantity and its relation to surface charge. , 1993, Physical review. B, Condensed matter.

[37]  K. Rabe,et al.  Physics of thin-film ferroelectric oxides , 2005, cond-mat/0503372.