TY - JOUR
T1 - Structural and thermodynamic limits of layer thickness in 2D halide perovskites
AU - Myae Soe, Chan Myae
AU - Nagabhushana, G. P.
AU - Shivaramaiah, Radha
AU - Tsai, Hsinhan
AU - Nie, Wanyi
AU - Blancon, Jean Christophe
AU - Melkonyan, Ferdinand
AU - Cao, Duyen H.
AU - Traoré, Boubacar
AU - Pedesseau, Laurent
AU - Kepenekian, Mikaël
AU - Katan, Claudine
AU - Even, Jacky
AU - Marks, Tobin J.
AU - Navrotsky, Alexandra
AU - Mohite, Aditya D.
AU - Stoumpos, Constantinos C.
AU - Kanatzidis, Mercouri G.
N1 - Publisher Copyright:
© 2019 National Academy of Sciences. All Rights Reserved.
PY - 2019/1/2
Y1 - 2019/1/2
N2 - In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)2(A)n−1MnX3n+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 (ΔHf), 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.
AB - In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)2(A)n−1MnX3n+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 (ΔHf), 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.
KW - Formation enthalpy
KW - Homologous series
KW - Layered compounds
KW - Perovskites
KW - Photovoltaics
KW - Ruddlesden–Popper halide
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U2 - 10.1073/pnas.1811006115
DO - 10.1073/pnas.1811006115
M3 - Article
C2 - 30563858
AN - SCOPUS:85059459063
SN - 0027-8424
VL - 116
SP - 58
EP - 66
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 1
ER -