Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†

Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi

doi:10.1016/0022-3697(90)90021-7

Cited by 485 publications

(663 citation statements)

References 27 publications

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“…Within the Rayleigh scattering model, the associated relaxation rate is taken to be temperature independent, Due to the very large unit cell 990.0(4) Å 3 11 , it is natural to expect rather low Debye temperatures for various acoustic phonon modes in MAPbI 3 . Indeed, the results of the calorimetric study predict that the range of Debye temperatures is between 80 and 220 K for MAPbX 3 (X=Cl, Br, I) compounds 16 . Although for our SC samples some improvements of fits are obtained by using higher Debye temperatures 6 7 in Eq.…”

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confidence: 99%

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH₃NH₃PbI₃

Pisoni

Jaćimović

Barišić

et al. 2014

J. Phys. Chem. Lett.

460

465

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We report on the temperature dependence of thermal conductivity of single crystalline and polycrystalline organometallic perovskite CH3NH3PbI3. The comparable absolute values and temperature dependence of the two samples’ morphologies indicate the minor role of the grain boundaries on the heat transport. Theoretical modeling demonstrates the importance of the resonant scattering in both specimens. The interaction between phonon waves and rotational degrees of freedom of CH3NH3 + sublattice emerges as the dominant mechanism for attenuation of heat transport and for ultralow thermal conductivity of 0.5 W/(Km) at room temperature.

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confidence: 99%

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH₃NH₃PbI₃

Pisoni

Jaćimović

Barišić

et al. 2014

J. Phys. Chem. Lett.

460

465

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“…Therefore, a transient intermediate phase has been postulated, but not yet been resolved. 26 The behavior of the "A-cation" CH 3 NH 3 + , which, other than in purely inorganic perovskites, possesses several rotational degrees of freedom in the high-temperature phase, has been investigated by means of NMR-spectroscopy 27 as well as IR-vibrational spectroscopy, 28 calorimetry, 28 and dielectric measurements. 24,29 It was found that the cubic symmetry of the high-temperature phase is effectively preserved through rapid random reorientations of the CH 3 NH 3 + -cation.…”

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confidence: 99%

“…Eventually, in the orthorhombic phase, all degrees of freedom are frozen. 27,28 Information on optical and electronic properties of CH 3 NH 3 PbI 3 at low temperature is very scarce. Apart from the aforementioned dielectric studies reflecting the behavior of the CH 3 NH 3 + -cation, some data are available on resistivity showing a decrease with increasing temperature as is typical for undoped semiconductors.…”

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confidence: 99%

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

et al. 2014

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The optoelectronic properties of the mixed hybrid lead halide perovskite CH3NH3PbI3−xClx have been subject to numerous recent studies related to its extraordinary capabilities as an absorber material in thin film solar cells. While the greatest part of the current research concentrates on the behavior of the perovskite at room temperature, the observed influence of phonon-coupling and excitonic effects on charge carrier dynamics suggests that low-temperature phenomena can give valuable additional insights into the underlying physics. Here, we present a temperature-dependent study of optical absorption and photoluminescence (PL) emission of vapor-deposited CH3NH3PbI3−xClx exploring the nature of recombination channels in the room- and the low-temperature phase of the material. On cooling, we identify an up-shift of the absorption onset by about 0.1 eV at about 100 K, which is likely to correspond to the known tetragonal-to-orthorhombic transition of the pure halide CH3NH3PbI3. With further decreasing temperature, a second PL emission peak emerges in addition to the peak from the room-temperature phase. The transition on heating is found to occur at about 140 K, i.e., revealing significant hysteresis in the system. While PL decay lifetimes are found to be independent of temperature above the transition, significantly accelerated recombination is observed in the low-temperature phase. Our data suggest that small inclusions of domains adopting the room-temperature phase are responsible for this behavior rather than a spontaneous increase in the intrinsic rate constants. These observations show that even sparse lower-energy sites can have a strong impact on material performance, acting as charge recombination centres that may detrimentally affect photovoltaic performance but that may also prove useful for optoelectronic applications such as lasing by enhancing population inversion.

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“…Based on the molar heat capacity ( ) measurement by Onoda-Yamamuro et al 31 and the density ( ) of MAPbI3 15, 32 , we calculated the volumetric heat capacity = / , where the is the molar mass of the MAPbI3 (0.62 kg/mol). As shown Figure 3, the volumetric heat capacity of the pseudocubic MAPbI3 is even slightly smaller than its tetragonal counterpart except for the peak at phase change temperature 330 K. Therefore, the heat capacity should not be responsible for the predicted sudden increase in thermal conductivity from the tetragonal phase to the pseudocubic phase.…”

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confidence: 99%

“…The smaller the broadening of the SED peak, the longer the phonon lifetime. 31,35 In the tetragonal phase of MAPbI3, the optical phonon branches (see Figure 4a) are significantly broadened, indicating very short optical phonon lifetimes. The line shape of the optical braches are still distinguishable in the pseudocubic phase, meaning that the optical phonons in the pseudocubic structure have much longer lifetimes (see Figure 4b).…”

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confidence: 99%

Lattice thermal conductivity of organic-inorganic hybrid perovskite CH3NH3PbI3

Qian

Yang

2016

Applied Physics Letters

108

107

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Great success has been achieved in improving the photovoltaic energy conversion efficiency of the organic-inorganic hybrid perovskite-based solar cells, but with very limited knowledge on the thermal transport in hybrid perovskites, which could affect the device lifetime and stability. Based on the potential field derived from the density functional theory calculations, we studied the lattice thermal conductivity of the hybrid halide perovskite CH3NH3PbI3 using equilibrium molecular dynamics simulations.Temperature-dependent thermal conductivity is reported from 160 K to 400 K, which covers the tetragonal phase (160 -330 K) and the pseudocubic phase (>330 K). A very low thermal conductivity (0.59 W/m·K) is found in the tetragonal phase at room temperature, whereas a much higher thermal conductivity is found in the pseudocubic phase (1.80 W/m·K at 330K). The low group velocity of acoustic phonons and the strong anharmonicity are found responsible for the relatively low thermal conductivity of the tetragonal CH3NH3PbI3.

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Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†

Cited by 485 publications

References 27 publications

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH₃NH₃PbI₃

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH₃NH₃PbI₃

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

Lattice thermal conductivity of organic-inorganic hybrid perovskite CH3NH3PbI3

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Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†

Cited by 485 publications

References 27 publications

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH3NH3PbI3

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH3NH3PbI3

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

Lattice thermal conductivity of organic-inorganic hybrid perovskite CH3NH3PbI3

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Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH₃NH₃PbI₃

Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH₃NH₃PbI₃