TY - JOUR
T1 - Complete Dopant Substitution by Spinodal Decomposition in Mn-Doped Two-Dimensional CsPbCl3 Nanoplatelets
AU - Li, Zhi Jun
AU - Hofman, Elan
AU - Davis, Andrew Hunter
AU - Khammang, Alex
AU - Wright, Joshua T.
AU - Dzikovski, Boris
AU - Meulenberg, Robert W.
AU - Zheng, Weiwei
N1 - Funding Information:
W.Z. acknowledges support from the start-up grant of Syracuse University. TEM measurements were performed at the Cornell Center for Materials Research (CCMR), which is supported through the NSF MRSEC program (DMR-1719875). ACERT is supported by the National Institutes of Health Grant NIH/ NIBIB R010EB00315. W.Z. appreicates the valuble discussion on EPR with Prof. Kevin R. Kittilstved. W.Z. thanks Prof. Mathew M. Maye, Yuetian Chen, and Hediyeh Zamani for their help on the analysis of the size and thickness of the NPLs. We thank D. A. Driscoll at SUNY-ESF for help with ICP-OES measurements. The work at the University of Maine and Illinois Institute of Technology was supported by the National Science Foundation under Grant No. DMR-1708617. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. Portions of this research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/9/25
Y1 - 2018/9/25
N2 - The introduction of dopants plays a key role in the physical properties of semiconductors for optoelectronic applications. However, doping is generally challenging for nanocrystals (NCs), especially for two-dimensional (2D) NCs, due to the self-annealing effect and high surface energies required for dopant addition. Here, we report an efficient doping strategy for Mn-doped 2D CsPbCl3 (i.e., Mn:CsPbCl3) nanoplatelets (NPLs) through a postsynthetic solvothermal process. While the original lightly doped 2D Mn:CsPbCl3 NPLs were obtained from growth doping, higher Mn doping efficiencies were achieved through diffusion doping under pressure-mediated solvothermal conditions, resulting in enhanced Mn photoluminescence (PL). Surprisingly, a new CsMnCl3 phase with complete dopant substitution by spinodal decomposition was observed with extended solvothermal treatment, which is confirmed by powder X-ray diffraction, X-ray absorption fine structure, and electron paramagnetic resonance. Compared with Mn:CsPbCl3 NPLs, the pure CsMnCl3 NPLs give rise to shorter Mn PL lifetime, which is consistent with the short Mn-Mn distance within CsMnCl3 NPLs. This work provides an efficient strategy for doping inside NCs as well as new insights on the dopant concentration-dependent structural and optical properties of perovskite NCs.
AB - The introduction of dopants plays a key role in the physical properties of semiconductors for optoelectronic applications. However, doping is generally challenging for nanocrystals (NCs), especially for two-dimensional (2D) NCs, due to the self-annealing effect and high surface energies required for dopant addition. Here, we report an efficient doping strategy for Mn-doped 2D CsPbCl3 (i.e., Mn:CsPbCl3) nanoplatelets (NPLs) through a postsynthetic solvothermal process. While the original lightly doped 2D Mn:CsPbCl3 NPLs were obtained from growth doping, higher Mn doping efficiencies were achieved through diffusion doping under pressure-mediated solvothermal conditions, resulting in enhanced Mn photoluminescence (PL). Surprisingly, a new CsMnCl3 phase with complete dopant substitution by spinodal decomposition was observed with extended solvothermal treatment, which is confirmed by powder X-ray diffraction, X-ray absorption fine structure, and electron paramagnetic resonance. Compared with Mn:CsPbCl3 NPLs, the pure CsMnCl3 NPLs give rise to shorter Mn PL lifetime, which is consistent with the short Mn-Mn distance within CsMnCl3 NPLs. This work provides an efficient strategy for doping inside NCs as well as new insights on the dopant concentration-dependent structural and optical properties of perovskite NCs.
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U2 - 10.1021/acs.chemmater.8b02657
DO - 10.1021/acs.chemmater.8b02657
M3 - Article
AN - SCOPUS:85053244819
SN - 0897-4756
VL - 30
SP - 6400
EP - 6409
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 18
ER -