Dataset Information

The nature of hydrogen-bonding interaction in the prototypic hybrid halide perovskite, tetragonal CH3NH3PbI3.

ABSTRACT: In spite of the key role of hydrogen bonding in the structural stabilization of the prototypic hybrid halide perovskite, CH3NH3PbI3 (MAPbI3), little progress has been made in our in-depth understanding of the hydrogen-bonding interaction between the MA(+)-ion and the iodide ions in the PbI6-octahedron network. Herein, we show that there exist two distinct types of the hydrogen-bonding interaction, naming ?- and ?-modes, in the tetragonal MAPbI3 on the basis of symmetry argument and density-functional theory calculations. The computed Kohn-Sham (K-S) energy difference between these two interaction modes is 45.14 meV per MA-site with the ?-interaction mode being responsible for the stable hydrogen-bonding network. The computed bandgap (Eg) is also affected by the hydrogen-bonding mode, with Eg of the ?-interaction mode (1.73 eV) being significantly narrower than that of the ?-interaction mode (2.03 eV). We have further estimated the individual bonding strength for the ten relevant hydrogen bonds having a bond critical point.

SUBMITTER: Lee JH

PROVIDER: S-EPMC4759593 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

The nature of hydrogen-bonding interaction in the prototypic hybrid halide perovskite, tetragonal CH3NH3PbI3.

Lee June Ho JH Lee Jung-Hoon JH Kong Eui-Hyun EH Jang Hyun Myung HM

Scientific reports 20160219

In spite of the key role of hydrogen bonding in the structural stabilization of the prototypic hybrid halide perovskite, CH3NH3PbI3 (MAPbI3), little progress has been made in our in-depth understanding of the hydrogen-bonding interaction between the MA(+)-ion and the iodide ions in the PbI6-octahedron network. Herein, we show that there exist two distinct types of the hydrogen-bonding interaction, naming α- and β-modes, in the tetragonal MAPbI3 on the basis of symmetry argument and density-funct ...[more]

PMID: 26892429

Similar Datasets

Project description:The structural stability of the extensively studied organic-inorganic hybrid methylammonium tetrel halide perovskite semiconductors, MATtX3 (MA = CH3NH3+; Tt = Ge, Sn, Pb; X = Cl, Br, I), arises as a result of non-covalent interactions between an organic cation (CH3NH3+) and an inorganic anion (TtX3-). However, the basic understanding of the underlying chemical bonding interactions in these systems that link the ionic moieties together in complex configurations is still limited. In this study, ion pair models constituting the organic and inorganic ions were regarded as the repeating units of periodic crystal systems and density functional theory simulations were performed to elucidate the nature of the non-covalent interactions between them. It is demonstrated that not only the charge-assisted N-H···X and C-H···X hydrogen bonds but also the C-N···X pnictogen bonds interact to stabilize the ion pairs and to define their geometries in the gas phase. Similar interactions are also responsible for the formation of crystalline MATtX3 in the low-temperature phase, some of which have been delineated in previous studies. In contrast, the Tt···X tetrel bonding interactions, which are hidden as coordinate bonds in the crystals, play a vital role in holding the inorganic anionic moieties (TtX3-) together. We have demonstrated that each Tt in each [CH3NH3+•TtX3-] ion pair has the capacity to donate three tetrel (σ-hole) bonds to the halides of three nearest neighbor TtX3- units, thus causing the emergence of an infinite array of 3D TtX64- octahedra in the crystalline phase. The TtX44- octahedra are corner-shared to form cage-like inorganic frameworks that host the organic cation, leading to the formation of functional tetrel halide perovskite materials that have outstanding optoelectronic properties in the solid state. We harnessed the results using the quantum theory of atoms in molecules, natural bond orbital, molecular electrostatic surface potential and independent gradient models to validate these conclusions.

Project description:Organic-inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. High-efficiency solar cells can be produced with solution-processed active layers. The materials are earth abundant, and the simple processing required suggests that high-throughput and low-cost manufacture at scale should be possible. While these materials bear considerable similarity to traditional inorganic semiconductors, there are notable differences in their optoelectronic behavior. A key distinction of these materials is that they are physically soft, leading to considerable thermally activated motion. In this Account, we discuss the internal motion of methylammonium lead iodide (CH3NH3PbI3) and formamidinium lead iodide ([CH(NH2)2]PbI3), covering: (i) molecular rotation-libration in the cuboctahedral cavity; (ii) drift and diffusion of large electron and hole polarons; (iii) transport of charged ionic defects. These processes give rise to a range of properties that are unconventional for photovoltaic materials, including frequency-dependent permittivity, low electron-hole recombination rates, and current-voltage hysteresis. Multiscale simulations, drawing from electronic structure, ab initio molecular dynamic and Monte Carlo computational techniques, have been combined with neutron diffraction measurements, quasi-elastic neutron scattering, and ultrafast vibrational spectroscopy to qualify the nature and time scales of the motions. Electron and hole motion occurs on a femtosecond time scale. Molecular libration is a sub-picosecond process. Molecular rotations occur with a time constant of several picoseconds depending on the cation. Recent experimental evidence and theoretical models for simultaneous electron and ion transport in these materials has been presented, suggesting they are mixed-mode conductors with similarities to fast-ion conducting metal oxide perovskites developed for battery and fuel cell applications. We expound on the implications of these effects for the photovoltaic action. The temporal behavior displayed by hybrid perovskites introduces a sensitivity in materials characterization to the time and length scale of the measurement, as well as the history of each sample. It also poses significant challenges for accurate materials modeling and device simulations. There are large differences between the average and local crystal structures, and the nature of charge transport is too complex to be described by common one-dimensional drift-diffusion models. Herein, we critically discuss the atomistic origin of the dynamic processes and the associated chemical disorder intrinsic to crystalline hybrid perovskite semiconductors.

Dataset Information

The nature of hydrogen-bonding interaction in the prototypic hybrid halide perovskite, tetragonal CH3NH3PbI3.

Publications

The nature of hydrogen-bonding interaction in the prototypic hybrid halide perovskite, tetragonal CH3NH3PbI3.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets