Phase transitions and crystal dynamics in the cubic perovskite CH3NH3PbCl3

Maalej, A.; Abid, Y.; Kallel, A.; Daoud, A.; Lautié, A.; Romain, F.

doi:10.1016/s0038-1098(97)00199-3

Cited by 97 publications

(99 citation statements)

References 17 publications

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“…The optimized structures of O-CH 3 NH 3 PbI 3 and T-CH 3 NH 3 PbI 3 respectively are obtained and the lattice constants are listed in Table 1, where measured and earlier predicted values on CH 3 NH 3 PbI 3 are inserted too for comparison. It is seen that our calculated data are roughly consistent with those measured and earlier predicted values, indicating the reliability of the present computational scheme2526. To the conventional stage, such differences are reasonably acceptable due to the relatively loose organic-inorganic hybrid structure.…”

Section: Resultssupporting

confidence: 87%

Electronic structure of organometal halide perovskite CH3NH3BiI3 and optical absorption extending to infrared region

Zhu

Liu

2016

Sci Rep

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The electronic structure and optical absorption spectrum of organometal halide perovskite compound CH3NH3BiI3 as a substituting candidate of well-concerned CH3NH3PbI3 not only for environmental friendly consideration are studied using the first principles calculations. It is revealed that a Bi replacement of Pb in CH3NH3PbI3 does not change seriously the band edge structure but the bandgap becomes narrow. Consequently, CH3NH3BiI3 exhibits not only stronger visible light absorption than CH3NH3PbI3 does but more strong absorption in the infrared region, which is however absent in CH3NH3PbI3. It is suggested that CH3NH3BiI3 may be one of even more promising alternatives to CH3NH3PbI3 for spectrum-broad and highly-efficient solar cells.

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Section: Resultssupporting

confidence: 87%

Electronic structure of organometal halide perovskite CH3NH3BiI3 and optical absorption extending to infrared region

Zhu

Liu

2016

Sci Rep

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“…The peak at ≈ 320 cm −1 , observed in both bromide crystals (supporting information), appears to correspond to a 480 cm −1 peak in CH 3 NH 3 PbCl 3 . [20] The frequency ratio here is about 1.5, in agreement with what would be expected for a simple harmonic oscillator model using only halide masses. The fact that this 320 cm −1 peak exists both in CH 3 NH 3 PbBr 3 and CsPbBr 3 , and that the frequency ratio agrees with harmonic oscillators with halide masses, suggest that this mode is related to halide motion, and not the CH 3 torsion as previously suggested.…”

supporting

confidence: 87%

“…The fact that this 320 cm −1 peak exists both in CH 3 NH 3 PbBr 3 and CsPbBr 3 , and that the frequency ratio agrees with harmonic oscillators with halide masses, suggest that this mode is related to halide motion, and not the CH 3 torsion as previously suggested. [20] Peaks at 910 cm −1 , 969 cm −1 , in the 2890-2970 cm −1 range, and around 3100 cm −1 appear only in CH 3 NH 3 PbBr 3 ( Figure 1c), and are assigned to NH 3 wagging, C-N stretch, C-H stretch and N-H stretch, respectively. [21] These internal CH 3 NH 3 PbBr 3 modes show an abrupt broadening and intensity decrease at the same temperature ( ≈ 150 K) where the abrupt orthorhombic-tetragonal phase transition occurs in the low-frequency Raman spectra, indicating that the phase transition is coupled to the disordered motion of the CH 3 NH 3 PbBr 3 .…”

mentioning

confidence: 99%

Interplay between organic cations and inorganic framework and incommensurability in hybrid lead-halide perovskite CH3NH3PbBr3

Guo

Yaffe

Paley

et al. 2017

Phys. Rev. Materials

109

107

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Organic-inorganic coupling in the hybrid lead-halide perovskite is a central issue in rationalizing the outstanding photovoltaic performance of these emerging materials. Here we compare and contrast the evolution of structure and dynamics of the hybrid CH3NH3PbBr3 and the inorganic CsPbBr3 lead-halide perovskites with temperature, using Raman spectroscopy and single-crystal Xray diffraction. Results reveal a stark contrast between their order-disorder transitions, abrupt for the hybrid whereas smooth for the inorganic perovskite. X-ray diffraction observes an intermediate incommensurate phase between the ordered and the disordered phases in CH3NH3PbBr3. Lowfrequency Raman scattering captures the appearance of a sharp soft mode in the incommensurate phase, ascribed to the theoretically predicted amplitudon mode. Our work highlights the interaction between the structural dynamics of organic cation CH3NH + 3 and the lead-halide framework, and unravels the competition between tendencies of the organic and inorganic moieties to minimize energy in the incommensurate phase of the hybrid perovskite structure.Organic-inorganic hybrid lead-halide perovskites have emerged as a promising class of new generation photovoltaic materials [1][2][3], showing excellent electronic properties and outstanding power conversion efficiencies [4]. Fundamental insight of the structural dynamics holds the key to understanding their unique electronic properties, and is the subject of intensive theoretical and experimental investigations.[5-10] Methylammonium cation (CH 3 NH + 3 , MA), the most frequently incorporated A site cation in recent photovoltaic applications, possesses a large dipole and exhibits dynamic orientational disorder at room temperature. [11,12] The orientational degrees of freedom of the anisotropic organic cation have been suggested to be responsible for the excellent electronic properties of the hybrid perovskites. [13][14][15]. Yet the inorganic lead-halide framework is the actual optically and electronically active component, on which charge carriers reside. A gap of knowledge exists on how the structural dynamics of MA and lead-halide framework couple with each other despite intensive investigations.In this Letter, we focus on unravelling the interplay between organic MA cations and the inorganic leadhalide framework, and highlight the unique signatures of such coupling. Here we report drastically different phase transformation behaviors between hybrid and inorganic lead-halide perovskites. Using low-frequency Raman scattering, we observe that there is an intermediate structural phase in CH 3 NH 3 PbBr 3 between the orthorhombic and tetragonal phases. With single-crystal X-ray diffraction, we conclude that the intermediate state to be an incommensurate phase, and we follow the evolution of the incommensurate modulation wave vector as * mpimenta@fisica.ufmg.br a function of temperature. A newly activated Raman mode of the incommensurate phase is assigned to the vibration in the amplitude of the structural modulation (...

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“…These results demonstrate that, in spite of the expected reliability of SOC-GW calculations, a static picture based on the optimized structures is not able to explain the experimental data for the tetragonal-cubic phase transition. observed a signal at 66 cm -1 in the Raman spectrum of the high temperature phase of MAPbCl 3 , that, due to symmetry reasons, should be silent 47. XRD studies by Mashiyama et.…”

mentioning

confidence: 92%

Structural and optical properties of methylammonium lead iodide across the tetragonal to cubic phase transition: implications for perovskite solar cells

Quarti

Mosconi

Ball

et al. 2016

Energy Environ. Sci.

472

393

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photovoltaic properties of MAPbI 3 perovskites across the tetragonal to cubic transition, due to structural fluctuations on a sub-picosecond timescale that make the instantaneous electronic energy levels and band-gap of the formally cubic, high temperature structure, to differ only slightly from those of the room temperature stable tetragonal phase. disordered position of the Cl anions 45 and the presence of a Raman signal at 66 cm -1 in the high temperature phase of MAPbCl 3 . 47 From a technological perspective, these results help to explain the lack of an observable abrupt change in photovoltaic device performance above room temperature 23 as would be expected to be observable if the light-harvester undergoes a phase transition. This is also further evidence indicating that ferroelectricity contributions to the optoelectronic properties, as in traditional inorganic materials, 54-57 are negligible, since the ferroelectric polarizability is expected to change dramatically across the transition between two different crystalline structures.On the contrary, this view supports other proposed mechanisms, as the spatial charge localization 50, 58 and/or stable band bending effects at the interfaces and grain boundaries, 59 as the basis of the impressive inherent performance of hybrid lead halide perovskites. ASSOCIATED CONTENT Supplementary InformationExperimental methods; theoretical methods and models; EQE measurements on different MAPbI3 devices; corresponding JV measurements of the devices; EQE of a cell with MAPbI 3-xClx ; comparison between theoretical and experimental radial distribution function of MAPbI 3 perovskite; theoretical fluctuation of the band edges.

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Phase transitions and crystal dynamics in the cubic perovskite CH3NH3PbCl3

Cited by 97 publications

References 17 publications

Electronic structure of organometal halide perovskite CH3NH3BiI3 and optical absorption extending to infrared region

Electronic structure of organometal halide perovskite CH3NH3BiI3 and optical absorption extending to infrared region

Interplay between organic cations and inorganic framework and incommensurability in hybrid lead-halide perovskite CH3NH3PbBr3

Structural and optical properties of methylammonium lead iodide across the tetragonal to cubic phase transition: implications for perovskite solar cells

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