Structural Phase Transitions of Hybrid Perovskites CH3NH3PbX3 (X = Br, Cl) from Synchrotron and Neutron Diffraction Data

López, Carlos A.; Álvarez-Galván, M. Consuelo; Abia, Carmen; Fernández‐Díaz, M. T.

doi:10.5772/intechopen.91421

Cited by 2 publications

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“…On the other hand, the phase transition temperature to phase I increases with increasing fraction of Cl – , and for x < 1.33, the sample decomposition occurs before the crystals reach the cubic phase. On this point, it should be emphasized that these results are opposite to those found for MAPbBr x Cl 3– x systems, in which the increase of the Cl fraction induces a stabilization of the Pm 3̅ m phase at lower temperatures …”

Section: Resultscontrasting

confidence: 58%

Three-Dimensional Methylhydrazinium Lead Halide Perovskites: Structural Changes and Effects on Dielectric, Linear, and Nonlinear Optical Properties Entailed by the Halide Tuning

et al. 2022

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Three-dimensional lead halide perovskites are promising materials for optoelectronic applications. The most famous representative comprise methylammonium (MA + ) and formamidinium (FA + ) cations, but recently, this group was enlarged by methylhydrazinium (MHy + ) analogues that crystallize in polar structures at room-temperature. Properties of threedimensional (3D) perovskites can be tuned by mixing of molecular cations or halide anions. Here, we report synthesis and physicochemical characterization of mixed-halide MHyPbBr x Cl 3−x (x = 0.40, 0.58, 0.85, 1.33, 1.95, 2.25, and 2.55) and MHyPbBr 2.8 I 0.2 perovskites. X-ray diffraction data show that all materials feature a polar monoclinic P2 1 symmetry at room temperature. With the temperature increase, all MHyPbBr x Cl 3−x perovskites undergo a displacive phase transition to another polar orthorhombic Pb2 1 m phase at T 2 ≥ 318 K. The bromine rich crystals (x ≥ 1.33) exhibit an additional order−disorder phase transition to the archetypal cubic Pm3̅ m phase at T 1 ≥ 409 K. In contrast to MHyPbBr x Cl 3−x perovskites, MHyPbBr 2.8 I 0.2 undergoes a direct P2 1 to Pm3̅ m phase transition. The temperature at which the cubic phase is stabilized, stability range of the Pb2 1 m phase, and distortion of the leadhalide octahedra decrease with the increase of Br − content. The structural changes affect dielectric, conductivity, and optical properties. In particular, the Br-rich samples show switchable dielectric behavior near 410−420 K. Furthermore, the activation energy of Cl − ionic conductivity increases with the increase of Br − content in phases Pb2 1 m and P2 1 , whereas in phase Pm3̅ m, the conductivity of Br − ions increases with the increase of Cl − content. The energy band gap narrows and the photoluminescence (PL) bands exhibit red shift when going from Cl to Br and then to I. Interestingly, whereas PL of the Br-rich and Cl-rich samples is dominated by bound exciton and self-trapped exciton bands, respectively, these bands are suppressed for 2.25 ≥ x ≥ 0.85. The PL color is strongly tuned by doping and changes from greenish-blue for the Cl-rich samples to yellowish-green for MHyPbBr 2.8 I 0.2 . SHG studies demonstrate that doping of MHyPbCl 3 with Br − ions reduces the difference between SHG signal intensities of the monoclinic and orthorhombic phases, to the extent that beyond x = 1.95, the SHG response of these phases becomes essentially the same. The relative SHG efficiencies of Br−Cl mixed materials at room temperature increase with the increase in Br content.

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Section: Resultscontrasting

confidence: 58%

Three-Dimensional Methylhydrazinium Lead Halide Perovskites: Structural Changes and Effects on Dielectric, Linear, and Nonlinear Optical Properties Entailed by the Halide Tuning

et al. 2022

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Enhanced stability in CH3NH3PbI3 hybrid perovskite from mechano-chemical synthesis: structural, microstructural and optoelectronic characterization

López

Abia

Rodrigues

et al. 2020

Sci Rep

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Among the hybrid organic–inorganic perovskites MAPbX3 (MA: methyl-ammonium CH3–NH3+, X = halogen), the triiodide specimen (MAPbI3) is still the material of choice for solar energy applications. Although it is able to absorb light above its 1.6 eV bandgap, its poor stability in humid air atmosphere has been a major drawback for its use in solar cells. However, we discovered that this perovskite can be prepared by ball milling in a straightforward way, yielding specimens with a superior stability. This fact allowed us to take atomic-resolution STEM images for the first time, with sufficient quality to unveil microscopic aspects of this material. We demonstrated full Iodine content, which might be related to the enhanced stability, in a more compact PbI6 framework with reduced unit-cell volume. A structural investigation from neutron powder diffraction (NPD) data of an undeuterated specimen was essential to determine the configuration of the organic MA unit in the 100–298 K temperature range. A phase transition is identified, from the tetragonal structure observed at RT (space group I4/mcm) to an orthorhombic (space group Pnma) phase where the methyl-ammonium organic units are fully localized. Our NPD data reveal that the MA changes are gradual and start before reaching the phase transition. Optoelectronic measurements yield a photocurrent peak at an illumination wavelength of 820 nm, which is redshifted by 30 nm with respect to previously reported measurements on MAPbI3 perovskites synthesized by crystallization from organic solvents.

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Structural Phase Transitions of Hybrid Perovskites CH₃NH₃PbX₃ (X = Br, Cl) from Synchrotron and Neutron Diffraction Data

Cited by 2 publications

References 56 publications

Three-Dimensional Methylhydrazinium Lead Halide Perovskites: Structural Changes and Effects on Dielectric, Linear, and Nonlinear Optical Properties Entailed by the Halide Tuning

Three-Dimensional Methylhydrazinium Lead Halide Perovskites: Structural Changes and Effects on Dielectric, Linear, and Nonlinear Optical Properties Entailed by the Halide Tuning

Enhanced stability in CH3NH3PbI3 hybrid perovskite from mechano-chemical synthesis: structural, microstructural and optoelectronic characterization

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