Structural and thermodynamic limits of layer thickness in 2D halide perovskites

Soe, Chan Myae Myae; Nagabhushana, G. P.; Shivaramaiah, Radha; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Melkonyan, Ferdinand; Cao, Duyen H.; Traoré, Boubacar; Pedesseau, Laurent; Kepenekian, Mikaël; Katan, Claudine; Even, Jacky; Marks, Tobin J.; Navrotsky, Alexandra; Mohite, Aditya D.; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.

doi:10.1073/pnas.1811006115

Structural and thermodynamic limits of layer thickness in 2D halide perovskites

Journal Article · Tue Dec 18 04:00:00 UTC 2018 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1811006115· OSTI ID:1576006

Soe, Chan Myae Myae; Nagabhushana, G. P.; Shivaramaiah, Radha; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; ; Cao, Duyen H.; Traoré, Boubacar; ; ; Katan, Claudine; ; ; ; Mohite, Aditya D.; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A')₂(A)_n-1M_nX_3n+1[where A = Cs⁺, CH₃NH₃⁺, HC(NH₂)₂⁺; A' = ammonium cation acting as spacer; M = Ge²⁺, Sn²⁺, Pb²⁺; and X = Cl^-, Br^-, I^-] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the nvalue defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH₃(CH₂)₂NH₃)₂(CH₃NH₃)₅Pb₆I₁₉(n= 6) and (CH₃(CH₂)₂NH₃)₂(CH₃NH₃)₆Pb₇I₂₂(n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH₃(CH₂)₂NH₃)₂(CH₃NH₃)₈Pb₉I₂₈” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔH_f), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.

Research Organization:: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US); Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of California, Davis, CA (United States); Northwestern Univ., Evanston, IL (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); US Department of the Navy, Office of Naval Research (ONR)

DOE Contract Number:: 89233218CNA000001; AC02-06CH11357; FG02-03ER46053; SC0001059

OSTI ID:: 1576006

Report Number(s):: LA-UR--19-20438

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 1 Vol. 116; ISSN 0027-8424

Publisher:: National Academy of Sciences

Country of Publication:: United States

Language:: ENGLISH

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