Cation Role in Structural and Electronic Properties of 3D Organic–Inorganic Halide Perovskites: A DFT Analysis

Moving from a general revise of the structural and electronic properties of the 3D methylammoniumtrihalogenoplumbates (MAPbX3, X = Cl, Br, I) class of halide organic–inorganic perovskites, we have focused our attention on the organic cation and studied the role it plays in the electronic/optical features of this class of compounds, paying attention mainly to the iodide compound. We found good agreement with previous experimental works, but at the same time we observed that the bare inorganic network [PbX3]− does not fully take into account the electronic properties of 3D systems. A comparison is performed between the electronic properties of MAPbI3 organic–inorganic perovskite and those of the purely inorganic CsPbI3. Furthermore, we show that hybrid methods applied on top of the spin–orbit calculated structures are not able to open the bandgap sufficiently to reproduce the experimental value, revealing the need of further and more computationally demanding procedures to get improved agreement.

[1]  J. Even,et al.  Electronic properties of 2D and 3D hybrid organic/inorganic perovskites for optoelectronic and photovoltaic applications , 2014 .

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

[3]  Aron Walsh,et al.  Electronic structure of hybrid halide perovskite photovoltaic absorbers , 2014, 1401.6993.

[4]  J. Even,et al.  DFT and k · p modelling of the phase transitions of lead and tin halide perovskites for photovoltaic cells , 2014 .

[5]  Hiroshi Segawa,et al.  Small Photocarrier Effective Masses Featuring Ambipolar Transport in Methylammonium Lead Iodide Perovskite: A Density Functional Analysis. , 2013, The journal of physical chemistry letters.

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

[7]  P. Umari,et al.  Relativistic Solar Cells , 2013, 1309.4895.

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

[9]  J. Even,et al.  Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications , 2013 .

[10]  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.

[11]  Michael Grätzel,et al.  First-Principles Modeling of Mixed Halide Organometal Perovskites for Photovoltaic Applications , 2013 .

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

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

[14]  J. Teuscher,et al.  Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites , 2012, Science.

[15]  Peng Gao,et al.  Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells. , 2012, Journal of the American Chemical Society.

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

[17]  Hao Li,et al.  CsSnI3: Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions. , 2012, Journal of the American Chemical Society.

[18]  Iftikhar Ahmad,et al.  First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M¼Cl, Br, I) , 2011 .

[19]  Koji Yamada,et al.  Tunable Perovskite Semiconductor CH3NH3SnX3 (X: Cl, Br, or I) Characterized by X-ray and DTA , 2011 .

[20]  Kiyoyuki Terakura,et al.  Charge-transport in tin-iodide perovskite CH3NH3SnI3: origin of high conductivity. , 2011, Dalton transactions.

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

[22]  D. Trots,et al.  High-temperature structural evolution of caesium and rubidium triiodoplumbates , 2008 .

[23]  Gustavo E. Scuseria,et al.  Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] , 2006 .

[24]  C. H. Park,et al.  First-Principles Study of the Structural and the Electronic Properties of the Lead-Halide-Based Inorganic-Organic perovskites (CH3NH3)PbX3 and CsPbX3 (X = Cl, Br, I) , 2004 .

[25]  Chang Yoon,et al.  Linear Network Model of Gene Regulation for the Yeast Cell Cycle , 2004 .

[26]  Takashi Kondo,et al.  Comparative study on the excitons in lead-halide-based perovskite-type crystals CH3NH3PbBr3 CH3NH3PbI3 , 2003 .

[27]  G. Scuseria,et al.  Hybrid functionals based on a screened Coulomb potential , 2003 .

[28]  K. Asai,et al.  Electronic structures of lead iodide based low-dimensional crystals , 2003 .

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

[30]  P. Blöchl,et al.  Projector augmented wave method:ab initio molecular dynamics with full wave functions , 2002, cond-mat/0201015.

[31]  D. Mitzi,et al.  Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer. , 2000, Inorganic chemistry.

[32]  Cherie R. Kagan,et al.  Organic-inorganic hybrid materials as semiconducting channels in thin-film field-effect transistors , 1999, Science.

[33]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[34]  K. Burke,et al.  Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] , 1997 .

[35]  G. Papavassiliou,et al.  Three- and low-dimensional inorganic semiconductors , 1997 .

[36]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[37]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[38]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[39]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[40]  D. Mitzi,et al.  Conducting tin halides with a layered organic-based perovskite structure , 1994, Nature.

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

[42]  L. Orgel,et al.  Stereochemistry of Cupric Compounds , 1957, Nature.