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

Abstract

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′) 2 (A) n −1 M n X 3 n +1 [where A = Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ; A′ = ammonium cation acting as spacer; M = Ge 2+ , Sn 2+ , Pb 2+ ; 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 -membersmore » yet, namely (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 5 Pb 6 I 19 ( n = 6) and (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 6 Pb 7 I 22 ( n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 8 Pb 9 I 28 ” (“ n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (Δ H 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.« less

Authors:
; ; ; ; ; ; ORCiD logo; ; ; ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo; ORCiD logo; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Laboratoy (ANL), Argonne, IL (United States); Univ. of California, Davis, CA (United States); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1487311
Alternate Identifier(s):
OSTI ID: 1566665
Grant/Contract Number:  
SC001059; 08SPCE973; 2017-A0010907682; FG02-03ER46053; AC02-06CH11357; SC0001059
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 1; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); optics; phonons; photosynthesis (natural and artificial); bio-inspired; hydrogen and fuel cells; charge transport; magnetism and spin physics; materials and chemistry by design; mesostructured materials; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

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., and Kanatzidis, Mercouri G. Structural and thermodynamic limits of layer thickness in 2D halide perovskites. United States: N. p., 2018. Web. doi:10.1073/pnas.1811006115.
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. Structural and thermodynamic limits of layer thickness in 2D halide perovskites. United States. doi:10.1073/pnas.1811006115.
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., and Kanatzidis, Mercouri G. Tue . "Structural and thermodynamic limits of layer thickness in 2D halide perovskites". United States. doi:10.1073/pnas.1811006115.
@article{osti_1487311,
title = {Structural and thermodynamic limits of layer thickness in 2D halide perovskites},
author = {Soe, Chan Myae Myae and Nagabhushana, G. P. and Shivaramaiah, Radha and Tsai, Hsinhan and Nie, Wanyi and Blancon, Jean-Christophe and Melkonyan, Ferdinand and Cao, Duyen H. and Traoré, Boubacar and Pedesseau, Laurent and Kepenekian, Mikaël and Katan, Claudine and Even, Jacky and Marks, Tobin J. and Navrotsky, Alexandra and Mohite, Aditya D. and Stoumpos, Constantinos C. and Kanatzidis, Mercouri G.},
abstractNote = {In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′) 2 (A) n −1 M n X 3 n +1 [where A = Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ; A′ = ammonium cation acting as spacer; M = Ge 2+ , Sn 2+ , Pb 2+ ; 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 (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 5 Pb 6 I 19 ( n = 6) and (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 6 Pb 7 I 22 ( n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 8 Pb 9 I 28 ” (“ n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (Δ H 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.},
doi = {10.1073/pnas.1811006115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 1,
volume = 116,
place = {United States},
year = {2018},
month = {12}
}

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DOI: 10.1073/pnas.1811006115

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