Progressive Polytypism and Bandgap Tuning in Azetidinium Lead Halide Perovskites.

Mixed halide azetidinium lead perovskites AzPbBr3-xXx (X = Cl or I) were obtained by mechanosynthesis. With varying halide composition from Cl- to Br- to I-, the chloride and bromide analogues both form in the hexagonal 6H polytype while the iodide adopts the 9R polytype. An intermediate 4H polytype is observed for mixed Br/I compositions. Overall, the structure progresses from 6H to 4H to 9R perovskite polytype with varying halide composition. Rietveld refinement of the powder X-ray diffraction patterns revealed a linear variation in unit cell volume as a function of the average radius of the anion, which not only is observed within the solid solution of each polytype (according to Vegard's law) but also extends uniformly across all three polytypes. This is correlated to a progressive (linear) tuning of the bandgap from 3.43 to 2.00 eV. Regardless of halide, the family of azetidinium halide perovskite polytypes are highly stable, with no discernible change in properties over more than 6 months under ambient conditions.

[1]  F. Morrison,et al.  Compositional Variation in Hybrid Organic–Inorganic Lead Halide Perovskites: Kinetically versus Thermodynamically Controlled Synthesis , 2021, Chemistry of Materials.

[2]  T. Kondo,et al.  Crystal Systems and Lattice Parameters of CH3NH3Pb(I1-xBrx)3 Determined Using Single Crystals: Validity of Vegard's Law. , 2020, Inorganic chemistry.

[3]  Thomas G. Allen,et al.  Efficient tandem solar cells with solution-processed perovskite on textured crystalline silicon , 2020, Science.

[4]  J. Irvine,et al.  Bandgap bowing in a zero-dimensional hybrid halide perovskite derivative: spin–orbit coupling versus lattice strain , 2020 .

[5]  Zhenghong Lu,et al.  Managing grains and interfaces via ligand anchoring enables 22.3%-efficiency inverted perovskite solar cells , 2020 .

[6]  Liyuan Han,et al.  Stabilizing heterostructures of soft perovskite semiconductors , 2019, Science.

[7]  A. Llamas-Saiz,et al.  Hybrid lead halide [(CH3)2NH2]PbX3(X = Cl−and Br−) hexagonal perovskites with multiple functional properties , 2019, Journal of Materials Chemistry C.

[8]  R. E. Schaak,et al.  Tutorial on Powder X-ray Diffraction for Characterizing Nanoscale Materials. , 2019, ACS nano.

[9]  F. Morrison,et al.  Stable 6H Organic–Inorganic Hybrid Lead Perovskite and Competitive Formation of 6H and 3C Perovskite Structure with Mixed A Cations , 2019, ACS Applied Energy Materials.

[10]  T. Unold,et al.  The phase diagram of a mixed halide (Br, I) hybrid perovskite obtained by synchrotron X-ray diffraction , 2019, RSC advances.

[11]  K. Uvdal,et al.  Rational molecular passivation for high-performance perovskite light-emitting diodes , 2019, Nature Photonics.

[12]  Ingo Krossing,et al.  Recent improvements in DSR , 2018 .

[13]  A. Polimeni,et al.  Azetidinium lead iodide: synthesis, structural and physico-chemical characterization , 2018 .

[14]  Anuj Kumar Goyal,et al.  Origin of Pronounced Nonlinear Band Gap Behavior in Lead-Tin Hybrid Perovskite Alloys , 2018 .

[15]  Edward P. Booker,et al.  Maximizing and stabilizing luminescence from halide perovskites with potassium passivation , 2018, Nature.

[16]  Lei Zhang,et al.  Growth of mixed-halide perovskite single crystals , 2018 .

[17]  Luis Camacho,et al.  Large guanidinium cation mixed with methylammonium in lead iodide perovskites for 19% efficient solar cells , 2017, Nature Energy.

[18]  Jinsong Hu,et al.  Additive engineering for high-performance room-temperature-processed perovskite absorbers with micron-size grains and microsecond-range carrier lifetimes , 2017 .

[19]  P. Schouwink,et al.  The Many Faces of Mixed Ion Perovskites: Unraveling and Understanding the Crystallization Process , 2017 .

[20]  Florian Hoegl,et al.  Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals. , 2017, Nano letters.

[21]  Andrew L. Johnson,et al.  Azetidinium lead iodide for perovskite solar cells , 2017, 1703.07240.

[22]  M. Kanatzidis,et al.  Structure-Band Gap Relationships in Hexagonal Polytypes and Low-Dimensional Structures of Hybrid Tin Iodide Perovskites. , 2017, Inorganic chemistry.

[23]  Anders Hagfeldt,et al.  Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells , 2016 .

[24]  Tongzhen Wei,et al.  Tunable bandgap in hybrid perovskite CH3NH3Pb(Br3−yXy) single crystals and photodetector applications , 2016 .

[25]  T. Edvinsson,et al.  Chemical engineering of methylammonium lead iodide/bromide perovskites: tuning of opto-electronic properties and photovoltaic performance , 2015 .

[26]  D. Kabra,et al.  Band Gap Tuning of CH₃NH₃Pb(Br(1-x)Clx)₃ Hybrid Perovskite for Blue Electroluminescence. , 2015, ACS applied materials & interfaces.

[27]  Ingo Krossing,et al.  DSR: enhanced modelling and refinement of disordered structures with SHELXL , 2015, Journal of applied crystallography.

[28]  H. Rensmo,et al.  Chemical and Electronic Structure Characterization of Lead Halide Perovskites and Stability Behavior under Different Exposures—A Photoelectron Spectroscopy Investigation , 2015 .

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

[30]  G. Sheldrick.  Crystal structure refinement with SHELXL , 2015, Acta crystallographica. Section C, Structural chemistry.

[31]  G. Sheldrick.  SHELXT – Integrated space-group and crystal-structure determination , 2015, Acta crystallographica. Section A, Foundations and advances.

[32]  A. Spek.  PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. , 2015, Acta crystallographica. Section C, Structural chemistry.

[33]  J. Noh,et al.  Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. , 2013, Nano letters.

[34]  C. Randall,et al.  Band-gap nonlinearity in perovskite structured solid solutions , 2010 .

[35]  Richard J. Gildea,et al.  OLEX2: a complete structure solution, refinement and analysis program , 2009 .

[36]  Anthony L. Spek,et al.  Structure validation in chemical crystallography , 2009, Acta crystallographica. Section D, Biological crystallography.

[37]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[38]  R. D. Shannon.  Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .