Self‐Organized Superlattice and Phase Coexistence inside Thin Film Organometal Halide Perovskite

Organometal halide perovskites have attracted widespread attention as the most favorable prospective material for photovoltaic technology because of their high photoinduced charge separation and carrier transport performance. However, the microstructural aspects within the organometal halide perovskite are still unknown, even though it belongs to a crystal system. Here direct observation of the microstructure of the thin film organometal halide perovskite using transmission electron microscopy is reported. Unlike previous reports claiming each phase of the organometal halide perovskite solely exists at a given temperature range, it is identified that the tetragonal and cubic phases coexist at room temperature, and it is confirmed that superlattices composed of a mixture of tetragonal and cubic phases are self-organized without a compositional change. The organometal halide perovskite self-adjusts the configuration of phases and automatically organizes a buffer layer at boundaries by introducing a superlattice. This report shows the fundamental crystallographic information for the organometal halide perovskite and demonstrates new possibilities as promising materials for various applications.

[1]  Lattice Thermal Conductivity of Organic-Inorganic Hybrid Perovskite CH3NH3PbI3 , 2015, 1512.09224.

[2]  A. Di Carlo,et al.  In situ observation of heat-induced degradation of perovskite solar cells , 2016, Nature Energy.

[3]  J. Keum,et al.  Perovskite Solar Cells with Near 100% Internal Quantum Efficiency Based on Large Single Crystalline Grains and Vertical Bulk Heterojunctions. , 2015, Journal of the American Chemical Society.

[4]  Wei Li,et al.  Direct observation of intrinsic twin domains in tetragonal CH3NH3PbI3 , 2017, Nature Communications.

[5]  G. Duscher,et al.  Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by in Situ TEM. , 2016, ACS applied materials & interfaces.

[6]  Alain Goriely,et al.  Morphological Control for High Performance, Solution‐Processed Planar Heterojunction Perovskite Solar Cells , 2014 .

[7]  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.

[8]  Laura M. Herz,et al.  Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber , 2013, Science.

[9]  T. Hansen,et al.  Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K. , 2015, Chemical communications.

[10]  Seonhee Lee,et al.  Self-formed grain boundary healing layer for highly efficient CH3NH3PbI3 perovskite solar cells , 2016, Nature Energy.

[11]  N. Park,et al.  Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% , 2012, Scientific Reports.

[12]  S. Uchida,et al.  Surface Treatment of the Compact TiO2 Layer for Efficient Planar Heterojunction Perovskite Solar Cells , 2015 .

[13]  Nam-Gyu Park,et al.  Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells. , 2014, Nature nanotechnology.

[14]  M. Johnston,et al.  Charge-carrier dynamics in vapour-deposited films of the organolead halide perovskite CH3NH3PbI3-xClx , 2014 .

[15]  M. Malac,et al.  Radiation damage in the TEM and SEM. , 2004, Micron.

[16]  Qi Chen,et al.  Planar heterojunction perovskite solar cells via vapor-assisted solution process. , 2014, Journal of the American Chemical Society.

[17]  P. Whitfield,et al.  Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide , 2016, Scientific Reports.

[18]  Chien-Yu Chen,et al.  Optical properties of organometal halide perovskite thin films and general device structure design rules for perovskite single and tandem solar cells , 2015 .

[19]  T. Oku,et al.  Fabrication and Characterization of TiO2/CH3NH3PbI3-based Photovoltaic Devices , 2014 .

[20]  Tsutomu Miyasaka,et al.  Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. , 2009, Journal of the American Chemical Society.

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

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

[23]  N. Park,et al.  Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH3CH2NH3)PbI3 , 2012, Nanoscale Research Letters.

[24]  Paul L. Burn,et al.  Electro-optics of perovskite solar cells , 2014, Nature Photonics.

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

[26]  Anders Hagfeldt,et al.  Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5ee03874j Click here for additional data file. , 2016, Energy & environmental science.

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

[28]  Sang Il Seok,et al.  High-performance photovoltaic perovskite layers fabricated through intramolecular exchange , 2015, Science.

[29]  Hiroshi Suga,et al.  Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II) , 1990 .

[30]  M. Grätzel,et al.  Sequential deposition as a route to high-performance perovskite-sensitized solar cells , 2013, Nature.

[31]  Henry J. Snaith,et al.  Efficient planar heterojunction perovskite solar cells by vapour deposition , 2013, Nature.

[32]  David B. Williams,et al.  Transmission Electron Microscopy , 1996 .

[33]  Gong Gu,et al.  High-Performance Flexible Perovskite Solar Cells by Using a Combination of Ultrasonic Spray-Coating and Low Thermal Budget Photonic Curing , 2015 .