TY - JOUR
T1 - Short Aromatic Diammonium Ions Modulate Distortions in 2D Lead Bromide Perovskites for Tunable White-Light Emission
AU - Fu, Ping
AU - Quintero, Michael A.
AU - Welton, Claire
AU - Li, Xiaotong
AU - Cucco, Bruno
AU - De Siena, Michael C.
AU - Even, Jacky
AU - Volonakis, George
AU - Kepenekian, Mikaël
AU - Liu, Runze
AU - Laing, Craig C.
AU - Klepov, Vladislav
AU - Liu, Yukun
AU - Dravid, Vinayak P.
AU - Manjunatha Reddy, G. N.
AU - Li, Can
AU - Kanatzidis, Mercouri G.
N1 - Funding Information:
This work was supported by the National Science Foundation under Grant No. DMR-2019444 (IMOD an NSF-STC). This work used the NUFAB facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, the Northwestern MRSEC program (NSF DMR-1720139), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through IIN. G.N.M.R. gratefully acknowledges financial support from ISITE international mobility grant, IR INFRANALYTICS FR2054, and EU H2020 (Grant 795091) for conducting the ssNMR experiments. P.F. acknowledges the financial support from the Chinese Academy of Science as a visiting scholar at Northwestern University, USA, 2020RQ036, and fruitful discussion with Chenjian Lin, Yanfeng Yin, and Paige Brown.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/11/8
Y1 - 2022/11/8
N2 - White-light broadband emission in the visible range from the low-dimensional halide perovskites is commonly attributed to structural distortions in lead bromide octahedra. In this paper, we report Dion-Jacobson-phase two-dimensional (2D) lead bromide perovskites based on short aromatic diammonium cations, p-phenylene diammonium (pPDA), m-phenylene diammonium (mPDA), and two 1D compounds templated by o-phenylene diammonium (oPDA). All of the compounds exhibit white-light emission. Single-crystal X-ray diffraction analysis reveals that the distortion of the Pb octahedra is influenced by the stereochemistry of the cations and their interactions with the perovskite layers. Solid-state 1H and 207Pb NMR spectroscopy analysis further confirms this trend, whereby different 1H and 207Pb chemical shifts are observed for the pPDA and mPDA spacer cations, indicating different hydrogen-bonding interactions and octahedral distortions. Owing to the octahedral distortion, 2D (mPDA)PbBr4compounds exhibit broader white-light emission than 2D (pPDA)PbBr4. Density functional theory calculations suggest that (pPDA)PbBr4and (mPDA)PbBr4are direct-band-gap semiconductors, and they exhibit larger electronic band gaps and effective masses than the Ruddlesden-Popper-phase (BA)2PbBr4. Among the films of these compounds, 2D (mPDA)PbBr4shows the best stability, which is attributed to stronger hydrogen-bonding interactions in the material.
AB - White-light broadband emission in the visible range from the low-dimensional halide perovskites is commonly attributed to structural distortions in lead bromide octahedra. In this paper, we report Dion-Jacobson-phase two-dimensional (2D) lead bromide perovskites based on short aromatic diammonium cations, p-phenylene diammonium (pPDA), m-phenylene diammonium (mPDA), and two 1D compounds templated by o-phenylene diammonium (oPDA). All of the compounds exhibit white-light emission. Single-crystal X-ray diffraction analysis reveals that the distortion of the Pb octahedra is influenced by the stereochemistry of the cations and their interactions with the perovskite layers. Solid-state 1H and 207Pb NMR spectroscopy analysis further confirms this trend, whereby different 1H and 207Pb chemical shifts are observed for the pPDA and mPDA spacer cations, indicating different hydrogen-bonding interactions and octahedral distortions. Owing to the octahedral distortion, 2D (mPDA)PbBr4compounds exhibit broader white-light emission than 2D (pPDA)PbBr4. Density functional theory calculations suggest that (pPDA)PbBr4and (mPDA)PbBr4are direct-band-gap semiconductors, and they exhibit larger electronic band gaps and effective masses than the Ruddlesden-Popper-phase (BA)2PbBr4. Among the films of these compounds, 2D (mPDA)PbBr4shows the best stability, which is attributed to stronger hydrogen-bonding interactions in the material.
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U2 - 10.1021/acs.chemmater.2c02471
DO - 10.1021/acs.chemmater.2c02471
M3 - Article
AN - SCOPUS:85140831900
SN - 0897-4756
VL - 34
SP - 9685
EP - 9698
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 21
ER -