Signatures of Coherent Phonon Transport in Ultralow Thermal Conductivity Two-Dimensional Ruddlesden–Popper Phase Perovskites

Christodoulides, Alexander D.; Guo, Peijun; Dai, Lingyun; Hoffman, Justin M.; Li, Xiaotong; Zuo, Xiaobing; Rosenmann, Daniel; Brumberg, Alexandra; Kanatzidis, Mercouri G.; Schaller, Richard D.; Malen, Jonathan A.

doi:10.1021/acsnano.0c03595

Signatures of Coherent Phonon Transport in Ultralow Thermal Conductivity Two-Dimensional Ruddlesden–Popper Phase Perovskites

Journal Article · Thu Mar 04 00:00:00 EST 2021 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.0c03595· OSTI ID:1864310

Christodoulides, Alexander D. ^[1]; ^[2]; Dai, Lingyun ^[1]; Hoffman, Justin M. ^[3]; ^[3]; Zuo, Xiaobing ^[4]; Rosenmann, Daniel ^[4]; ^[3]; ^[3]; ^[5]; ^[1]

Carnegie Mellon Univ., Pittsburgh, PA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Yale Univ., New Haven, CT (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)

An emerging class of methylammonium lead iodide (MAPbI₃)-based Ruddlesden-Popper (RP) phase perovskites, BA₂MA_n-1Pb_nI_3n+1 (n = 1-7), exhibit enhanced stability to environmental conditions relative to MAPbI₃, yet still degrade at elevated temperatures. Here, we experimentally determine the thermal conductivities of these layered RP phases for n = 1-6, where n defines the number of repeated perovskite octahedra per layer. We measure thermal conductivities of 0.37 ± 0.13/0.12, 0.17 ± 0.08/0.07, 0.21 ± 0.05/0.04, and 0.19 ± 0.04/0.03 W/m∙K in thin films of n = 1-4 and 0.08 ± 0.06/0.04, 0.06 ± 0.04/0.03, 0.06 ± 0.03/0.03, and 0.08 ± 0.07/0.04 W/m∙K in single crystals of n = 3-6. With the exception of n = 1, these thermal conductivities are lower than the range of 0.34-0.50 W/m∙K reported for single-crystal MAPbI₃. Reduced-order lattice dynamics modeling suggests that the initially decreasing trend of thermal conductivity in similarly oriented perovskites with increasing n may result from the transport properties of coherent phonons, emergent from the superstructure, that do not scatter at the interfaces of organic butylammonium chains and perovskite octahedra. Reduced group velocity of coherent phonons in n = 3-6, a consequence of band flattening in the phonon dispersion, is primarily responsible for their ultralow thermal conductivities. Similar effects on thermal conductivity have been experimentally demonstrated in deposited superlattices, but never in naturally defined materials such as RP phases. GIWAXS measurements reveal that higher n RP phase thin films are less orientationally controlled and therefore possess apparently elevated thermal conductivities relative to single crystals of the same n.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Army Research Office (ARO); US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1864310

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 3 Vol. 15; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Signatures of Coherent Phonon Transport in Ultralow Thermal Conductivity Two-Dimensional Ruddlesden–Popper Phase Perovskites

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