Non-monotonic Thermal Conductivity of FA_{x}MA_{1–x}PbI₃ Achieving Ultralow Values: The Role of Anharmonic Low Energy Rotation of Organic Moieties

Debasmita Pariari; Paribesh Acharyya; Arijit Sinha; Ashutosh Mohanty; Shaili Sett; Navkiranjot Kaur Gill; Arindam Ghosh; Umesh V. Waghmare; Kanishka Biswas; D. D. Sarma

doi:10.1021/acsenergylett.4c00047

journal article·2024-05-10

Non-monotonic Thermal Conductivity of FA_xMA_1–xPbI₃ Achieving Ultralow Values: The Role of Anharmonic Low Energy Rotation of Organic Moieties

Debasmita Pariari, Paribesh Acharyya, Arijit Sinha, Ashutosh Mohanty, Shaili Sett, Navkiranjot Kaur Gill, Arindam Ghosh, Umesh V. Waghmare, Kanishka Biswas, D. D. Sarma

ACS Energy Letters· Volume 9· Issue 5

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Abstract

Stability issues of MAPbI 3 and FAPbI 3 have led to the exploration of more stable FA x MA 1– x PbI 3 solid solutions for many energy applications. Thermal properties are important in view of the inevitable heat generation in energy conversion processes. MAPbI 3 is reported to have an ultralow thermal conductivity, κ (∼0.34 W·m –1 ·K –1 ). Surprisingly, there is no report of κ for FA/MA mixed compositions, despite their obvious relevance. Here, we report an intriguing observation of a non-monotonic reduction of κ with FA substitution, while most other physical properties, such as the lattice parameters and bandgap, vary monotonically. This leads the asymmetric composition FA 0.3 MA 0.7 PbI 3 to become the lowest κ (∼0.2 W·m –1 ·K –1 ) material among all three-dimensional metal halide perovskites. We show this non-monotonic κ is a consequence of two monotonic and opposing trends with increasing FA compositions, namely, an increasingly facile rotation of a decreasing number of MA ions. Raman studies, together with ab initio theoretical results, show that the heterogeneous bonding environment in FA x MA 1– x PbI 3 results in numerous low-energy, highly anharmonic, and localized optical phonon modes strongly coupled to acoustic phonons related exclusively to MA, but not FA, rotations, leading to very short phonon lifetimes (0.3–2 ps) and, therefore, to the ultralow κ for these compounds.

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Research context

Electronic materials

OpenAlex topics: Perovskite Materials and Applications · Advanced Thermoelectric Materials and Devices · Optical properties and cooling technologies in crystalline materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bengaluru 560012, India

New Chemistry Unit, School of Advanced Materials and International Centre for Materials Science, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P. O., Bengaluru 560064, India

Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P. O., Bengaluru 560064, India

Department of Physics, Indian Institute of Science, Bengaluru 560012, India

Centre for Nano Science and Engineering, Indian Institute of Science, Bengaluru 560012, India

School of Advanced Materials and International Centre for Materials Science, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P. O., Bengaluru 560064, India

Funding

Council of Scientific and Industrial Research, India · University Grants Commission · Science and Engineering Research Board · Mission on Nano Science and Technology · Department of Science and Technology, Ministry of Science and Technology, India · Jawaharlal Nehru Centre for Advanced Scientific Research

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