Structural and thermodynamic limits of layer thickness in 2D halide perovskites
In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)₂(A)n−1M n X3n+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...
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Published in | Proceedings of the National Academy of Sciences - PNAS Vol. 116; no. 1; pp. 58 - 66 |
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Main Authors | , , , , , , , , , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
National Academy of Sciences
02.01.2019
|
Series | PNAS Plus |
Subjects | |
Online Access | Get full text |
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Summary: | In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)₂(A)n−1M
n
X3n+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 n value 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. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 89233218CNA000001; AC02-06CH11357; FG02-03ER46053; SC0001059; N00014-17-1-2231 USDOE Office of Science (SC), Basic Energy Sciences (BES) US Department of the Navy, Office of Naval Research (ONR) LA-UR-19-20438 4Present address: Department of Materials Science and Technology, University of Crete, Heraklion GR-70013, Greece. 1C.M.M.S., G.P.N., and R.S. contributed equally to this work. Reviewers: A.K.C., University of Cambridge; and J.R.N., Colorado State University. Contributed by Alexandra Navrotsky, November 7, 2018 (sent for review July 2, 2018; reviewed by Anthony K. Cheetham and James R. Neilson) 3Present address: Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX 77005. Author contributions: C.M.M.S. and M.G.K. designed research; C.M.M.S., G.P.N., R.S., F.M., D.H.C., and C.C.S. performed research; H.T., W.N., J.-C.B., T.J.M., and A.D.M. contributed new reagents/analytic tools; C.M.M.S., R.S., F.M., D.H.C., B.T., L.P., M.K., C.K., J.E., and C.C.S. analyzed data; C.M.M.S., G.P.N., A.N., C.C.S., and M.G.K. wrote the paper; C.M.M.S., H.T., W.N., and J.-C.B. fabricated and characterized thin films; B.T., L.P., and M.K. performed DFT calculations; C.K. and J.E. supervised DFT calculations; T.J.M. supervised synthesis and characterization; A.N. consulted; A.D.M. supervised fabrication and characterization of thin films; C.C.S. and M.G.K. supervised the project. |
ISSN: | 0027-8424 1091-6490 |
DOI: | 10.1073/pnas.1811006115 |