Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites

Harwell, Jonathon R.; Payne, Julia L.; Sajjad, Muhammad T.; Heutz, Frank J. L.; Dawson, Daniel M.; Whitfield, Pamela S.; Irvine, John T. S.; Samuel, Ifor D. W.; Carpenter, Michael A.

doi:10.1103/physrevmaterials.2.065404

Cited by 21 publications

(31 citation statements)

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“…3,[21][22][23][24] Structural evolution of 3D LHPs and single-layered (n = 1) 2D LHPs with the absence of small A-site cations has been extensively investigated and shows interesting temperature-dependent transformations. [25][26][27][28][29][30] For example, 3D MAPbI3 perovskites adopt cubic, tetragonal, and orthorhombic phases at high, intermediate, and low temperatures, respectively. [25][26][27] On the other hand, the number of crystal phases and phase transition temperatures of single-layered (CmH2m+1NH3)2PbI4 (m = 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, and 18) are dependent on the chain length of the organic spacer.…”

Section: Introductionmentioning

confidence: 99%

“…[25][26][27][28][29][30] For example, 3D MAPbI3 perovskites adopt cubic, tetragonal, and orthorhombic phases at high, intermediate, and low temperatures, respectively. [25][26][27] On the other hand, the number of crystal phases and phase transition temperatures of single-layered (CmH2m+1NH3)2PbI4 (m = 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, and 18) are dependent on the chain length of the organic spacer. [28][29][30] Higher members (n ≥ 2) of 2D LHPs contain both organic spacers and A-site cations, and lie in between these two limits.…”

Section: Introductionmentioning

confidence: 99%

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Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

et al. 2019

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We report the cooling-induced crystallization of layered two-dimensional lead halide perovskites with controllable inorganic quantum-well thickness (n = 1, 2, 3, 4), organic spacer chain length (butyl-, pentyl-, hexylammonium), A-site cation (methylammonium, formamidinium), and halide anion (iodide, bromide). We report crystal structures for the iodide family as a function of these compositional parameters, and across their temperature dependent phase transitions. In general, lower symmetry crystal structures, increasing extents of organic-spacer interdigitation, and increasing organic-spacer corrugation tilts are observed at low temperature. In addition, greater structural distortions are seen in lead halide octahedra closest to the organic spacer layer, and larger-n structures exhibit periodic variation in Pb-I bond lengths. We also provide detailed guidance regarding the combination of synthetic parameters needed to achieve phase-pure crystals of each composition, and discuss difficulties encountered when trying to synthesize particular members of the 2D perovskite family containing formamidinium or cesium as the A-site cation. These results provide a foundation for understanding structural trends in 2D lead halide perovskites and the effect these trends have on their thermal, electrical, and optical properties.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

et al. 2019

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“…Among them, Brillouin light scattering is a nondestructive, noncontact method that is a powerful tool in the determination of the elastic constants, sound velocities, and acoustic attenuation coefficients of acoustic waves propagating in condensed matters [ 14 , 15 , 16 , 17 , 18 , 19 , 20 ]. Despite extensive studies on HOPs in terms of various experimental techniques, there are only a few acoustic studies on these materials [ 13 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ]. Various acoustic properties of CH 3 NH 3 PbX 3 (MAPbX 3 with X = Cl, Br, I) and CH(NH 2 ) 2 PbX 3 (FAPbX 3 with X = Cl, Br, I) have been reported at room temperature or as a function of temperature.…”

Section: Introductionmentioning

confidence: 99%

“…Significant elastic anisotropy was confirmed in MAPbBr 3 measured by the laser ultrasonic technique [ 13 ]. Harwell et al used resonant ultrasound spectroscopy to investigate the temperature dependence of acoustic resonant frequencies and the acoustic losses of methylammonium lead halide perovskites [ 25 ]. They found that acoustic losses are substantially large in the tetragonal phase of MAPbBr 3 and MAPbI 3 , which was attributed to the mobility of the ferroelastic twin walls.…”

Section: Introductionmentioning

confidence: 99%

“…They found that acoustic losses are substantially large in the tetragonal phase of MAPbBr 3 and MAPbI 3 , which was attributed to the mobility of the ferroelastic twin walls. The overall changes in the elastic properties were explained in terms of the MA order and disorder in each phase [ 25 ]. Zhevstovskikh et al used the ultrasonic technique to study the changes in the sound velocity and the attenuation coefficient of both the longitudinal and transverse acoustic waves of MAPbI 3 single crystals in the MHz range [ 27 ].…”

Section: Introductionmentioning

confidence: 99%

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Acoustic Anomalies and the Critical Slowing-Down Behavior of MAPbCl3 Single Crystals Studied by Brillouin Light Scattering

Lee

Naqvi

et al. 2022

Materials

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Inelastic light scattering spectra of organic–inorganic halide perovskite MAPbCl3 single crystals were investigated by using Brillouin spectroscopy. Sound velocities and acoustic absorption coefficients of longitudinal and transverse acoustic modes propagating along the cubic [100] direction were determined in a wide temperature range. The sound velocities exhibited softening upon cooling in the cubic phase, which was accompanied by the increasing acoustic damping. The obtained relaxation time showed a critical slowing-down behavior, revealing the order–disorder nature of the phase transition, which is consistent with the growth of strong central peaks upon cooling toward the phase transition point. The temperature dependences of the two elastic constants C11 and C44 were obtained in the cubic phase for the first time. The comparison of C11 and C44 with those of other halide perovskites showed that C11 of MAPbCl3 is larger and C44 is slightly smaller compared to the values of MAPbBr3 and MAPbI3. It suggests that MAPbCl3 has a more compact structure (smaller lattice constant) along with stronger binding forces, causing larger C11 and bulk modulus in this compound, and that the shear rigidity is exceedingly small similar to other halide perovskites. The reported elastic constants in this study may serve as a testbed for theoretical and calculational approaches for MAPbCl3.

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Highly Stable and Panchromatic Light Absorbing Cs₂OsX₆ (X = Cl⁻, Br⁻, I⁻) Vacancy Ordered Perovskites as Photoanodes for Solar Water Oxidation

Shanmugam

Halpati

Chandiran

2022

Adv Materials Inter

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In this work, osmium‐based vacancy‐ordered double perovskites Cs2OsX6 (X = Cl−, Br−, I−) are reported and the role of halides on stability, optical and photoelectrochemical properties is investigated. All these three materials crystallize in a cubic phase like Cs2SnX6 or Cs2PtX6 and possess extraordinary stability in ambient conditions and remain stable in strong acids and bases (from pH 1 to 11). One of the unique properties of these materials is that they show panchromatic visible and NIR absorption (up to 1200 nm) through ligand‐to‐metal [X (Cl−/Br−/I−) to Os] charge transfer and another NIR absorption between 1800 and 2500 nm due to Os d‐d transition. Their pH stability and panchromatic light absorption properties enabled them to be employed as photoanodes in PEC water‐splitting devices.

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Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites

Cited by 21 publications

References 61 publications

Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

Acoustic Anomalies and the Critical Slowing-Down Behavior of MAPbCl3 Single Crystals Studied by Brillouin Light Scattering

Highly Stable and Panchromatic Light Absorbing Cs₂OsX₆ (X = Cl⁻, Br⁻, I⁻) Vacancy Ordered Perovskites as Photoanodes for Solar Water Oxidation

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Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites

Cited by 21 publications

References 61 publications

Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites

Acoustic Anomalies and the Critical Slowing-Down Behavior of MAPbCl3 Single Crystals Studied by Brillouin Light Scattering

Highly Stable and Panchromatic Light Absorbing Cs2OsX6 (X = Cl−, Br−, I−) Vacancy Ordered Perovskites as Photoanodes for Solar Water Oxidation

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Product

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Highly Stable and Panchromatic Light Absorbing Cs₂OsX₆ (X = Cl⁻, Br⁻, I⁻) Vacancy Ordered Perovskites as Photoanodes for Solar Water Oxidation