Mobility driven thermoelectric and optical properties of two-dimensional halide-based hybrid perovskites: impact of organic cation rotation

Kagdada, Hardik L.; Gupta, Sanjeev K.; Sahoo, Satyaprakash; Singh, Dheeraj K.

doi:10.1039/d1cp05724c

Cited by 10 publications

(23 citation statements)

References 74 publications

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“…Density functional theory calculations of these materials with methylammonium cations frozen in different configurations reveal significant changes to the electronic properties (e.g., direct to indirect band gap transitions, mobility). 19 Molecular dynamics simulations using relatively simple pair-wise potentials reveal structure-dependent dynamics of the methylammonium reorientations, such that orientations become hindered for smaller "n", 17 consistent with the experimental results provided here. The neutron scattering results described in this contribution illustrate that increased layer thickness decreases the residence times of organic cation reorientations in layered hybrid halide perovskites and that the temperature-dependent rotational motion corresponds to longer time-resolved microwave conductivity lifetimes.…”

Section: ■ Introductionsupporting

confidence: 81%

Influence of Inorganic Layer Thickness on Methylammonium Dynamics in Hybrid Perovskite Derivatives

et al. 2022

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The layered Ruddlesden−Popper derivatives of CH 3 NH 3 PbI 3 have recently emerged as high-performing materials for photovoltaics with improved stability. The inclusion of organic molecules within the inorganic framework provides additional dynamic degrees of freedom that influence the optoelectronic properties. The rotational dynamics of CH 3 NH 3 + influence dielectric behavior and electronic excited-state dynamics in CH 3 NH 3 PbI 3 ; however, the influence of cation dynamics on properties in the layered derivatives has not yet been determined. We employ quasi-elastic neutron scattering to study the rotational dynamics of methylammonium (CH 3 NH 3 + , MA) and deuterated nb u t y l a m m o n i u m ( + CD (CD ) NH 3 2 3 3 , d -n B A ) i n ( d -nBA) 2 (MA) n−1 Pb n I 3n+1 (n = 2, 3). (d-nBA) 2 (MA) 2 Pb 3 I 10 exhibits shorter residence times of the CH 3 NH 3 + and + CD (CD ) NH 3 2 3 3 reorientational motions, which are attributed to the larger volumes that the cations occupy in the inorganic framework and to the dimensionality of the inorganic layer by way of dielectric screening between the organic cations. Discontinuities in the mean-squared displacement of overall hydrogen motion determined by fixedwindow elastic neutron scattering are consistent with phase transitions observed by differential scanning calorimetry and timeresolved microwave conductivity signals. Determining how the dimensionality of the inorganic layer influences the organic cation rotational dynamics provides fundamental chemical insight into how the electronic dynamics vary between n-members.

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Section: ■ Introductionsupporting

confidence: 81%

Influence of Inorganic Layer Thickness on Methylammonium Dynamics in Hybrid Perovskite Derivatives

et al. 2022

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“…The calculated Seebeck coefficients of all three structures at 300 K are higher than those obtained for other 2D and 3D Pbfree perovskites materials over a large carrier-concentration range. 17,18,48 On the other hand, the replacement of Pb through Sn provides higher electrical conductivity at room temperature. In addition, the increasing carrier concentration in all three structures results in a gradual rise in the electrical conductivity.…”

Section: Electronic Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…14,15 The crystal structure of 2D perovskites can be varied influencing electronic as well as optical properties, which makes them potential candidates for high-performance solar energy harvesting. [16][17][18] In spite of the now achieved excellent stability and performance, the toxicity of lead still limits the large-scale development of solar energy applications of 2D halide-based hybrid perovskite materials. Lead is a hazard to the environment and human health, which made researchers look for Pb-free solutions 19,20 by possible replacement through tin (Sn), germanium (Ge), bismuth (Bi), copper (Cu), silver (Ag), gold (Au), etc.…”

Section: Introductionmentioning

confidence: 99%

“…After complete elimination of Pb (AVA 2 (MA)Sn 2 I 7 ) the efficiency is again slightly reduced to 30.80%, which is still a better value than those reported for other perovskite materials. 15,17,18,36 At the same time of course the Pb-related toxicity has been completely removed.…”

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confidence: 99%

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Decreasing toxicity and increasing photoconversion efficiency by Sn-substitution of Pb in 5-ammonium valeric acid-based two-dimensional hybrid perovskite materials

Kagdada

Materny

Singh

2022

Phys. Chem. Chem. Phys.

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Tuning Thermal Conductivity of Hybrid Perovskites through Halide Alloying

Wang,

Fan,

Chen

et al. 2024

Advanced Science

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Tuning the thermal transport properties of hybrid halide perovskites is critical for their applications in optoelectronics, thermoelectrics, and photovoltaics. Here, an effective strategy is demonstrated to modulate the thermal transport property of hybrid perovskites by halide alloying. A highly tunable thermal conductivity of mixed‐halide hybrid perovskites is achieved due to halide‐alloying and structural distortion. The experimental measurements show that the room temperature thermal conductivity of MAPb(BrxI1‐x)3 (x = 0─1) can be largely modulated from 0.27 ± 0.07 W m−1 K−1 (x = 0.5) to 0.47 ± 0.09 W m−1 K−1 (x = 1). Molecular dynamics simulations further demonstrate that the thermal conductivity reduction of hybrid halide perovskites results from the suppression of the mean free paths of the low‐frequency acoustic and optical phonons. It is found that halide alloying and the induced structural distortion can largely increase the scatterings of optical and acoustic phonons, respectively. The confined diffusion of MA+ cations in the octahedra cage is found to act as an additional thermal transport channel in hybrid perovskites and can contribute around 10–20% of the total thermal conductivity. The findings provide a strategy for tailoring the thermal transport in hybrid halide perovskites, which may largely benefit their related applications.

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Mobility driven thermoelectric and optical properties of two-dimensional halide-based hybrid perovskites: impact of organic cation rotation

Abstract: The pivotal impact of organic cation rotation may render structural complexity in two-dimensional (2D) halide-based hybrid perovskites. The crucial role of the orientation of organic cation (MA = CH3NH3+) in...

Cited by 10 publications

References 74 publications

Influence of Inorganic Layer Thickness on Methylammonium Dynamics in Hybrid Perovskite Derivatives

Influence of Inorganic Layer Thickness on Methylammonium Dynamics in Hybrid Perovskite Derivatives

Decreasing toxicity and increasing photoconversion efficiency by Sn-substitution of Pb in 5-ammonium valeric acid-based two-dimensional hybrid perovskite materials

Tuning Thermal Conductivity of Hybrid Perovskites through Halide Alloying

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