Bulk Assembly of Zero-Dimensional Organic Lead Bromide Hybrid with Efficient Blue Emission
Abstract
Zero-dimensional (0D) organic metal halide hybrids are an emerging class of light emitting materials with exceptional photoluminescence quantum efficiencies (PLQEs), thanks to their perfect “host–guest” structures with light emitting metal halide species periodically “embedded” in a wide band gap organic cationic matrix through ionic bonds. However, achieving efficient blue emissions is challenging for this class of materials, as structural distortions of metal halides often lead to large Stokes shifts. Here we report a highly luminescent blue emitting 0D organic lead bromide, (C13H19N4)2PbBr4, with a peak emission of 460 nm (2.70 eV), a full width at half maximum (FWHM) of 66 nm (0.40 eV), a Stokes shift of 111 nm (0.85 eV), and a PLQE of ~40%. Single crystal structure analysis shows that individual PbBr42– species adopt a near-seesaw structure, which are coordinated to benzyl-hexamethylenetetrammonium (C13H19N4+) organic cations. The relatively small Stokes shift as compared to those of previously reported 0D organic metal halide hybrids are attributed to the low chemical reactivity of Pb 6s2 lone pairs and the rigid organic cationic matrix. Finally, (C13H19N4)2PbBr4 also shows exceptional stability in air with little-to-no change of properties for more than a year in ambient conditions.
- Authors:
-
[2];
[1];
[3];
[4]
- Florida State Univ., Tallahassee, FL (United States)
- FAMU-FSU College of Engineering, Tallahassee, FL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Florida State Univ., Tallahassee, FL (United States); FAMU-FSU College of Engineering, Tallahassee, FL (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1607040
- Grant/Contract Number:
- AC05-00OR22725; 17RT0906; DMR-1709116; CHE-1664661; DMR-1606952; DMR-1644779
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Materials Letters
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 6; Journal ID: ISSN 2639-4979
- Publisher:
- ACS Publications
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; anions; metals; inorganic compounds; cystal structure; halogens
Citation Formats
Lin, Haoran, Zhou, Chenkun, Chaaban, Maya, Xu, Liang-Jin, Zhou, Yan, Neu, Jennifer, Worku, Michael, Berkwits, Ella, He, Qingquan, Lee, Sujin, Lin, Xinsong, Siegrist, Theo, Du, Mao-Hua, and Ma, Biwu. Bulk Assembly of Zero-Dimensional Organic Lead Bromide Hybrid with Efficient Blue Emission. United States: N. p., 2019.
Web. doi:10.1021/acsmaterialslett.9b00333.
Lin, Haoran, Zhou, Chenkun, Chaaban, Maya, Xu, Liang-Jin, Zhou, Yan, Neu, Jennifer, Worku, Michael, Berkwits, Ella, He, Qingquan, Lee, Sujin, Lin, Xinsong, Siegrist, Theo, Du, Mao-Hua, & Ma, Biwu. Bulk Assembly of Zero-Dimensional Organic Lead Bromide Hybrid with Efficient Blue Emission. United States. https://doi.org/10.1021/acsmaterialslett.9b00333
Lin, Haoran, Zhou, Chenkun, Chaaban, Maya, Xu, Liang-Jin, Zhou, Yan, Neu, Jennifer, Worku, Michael, Berkwits, Ella, He, Qingquan, Lee, Sujin, Lin, Xinsong, Siegrist, Theo, Du, Mao-Hua, and Ma, Biwu. Mon .
"Bulk Assembly of Zero-Dimensional Organic Lead Bromide Hybrid with Efficient Blue Emission". United States. https://doi.org/10.1021/acsmaterialslett.9b00333. https://www.osti.gov/servlets/purl/1607040.
@article{osti_1607040,
title = {Bulk Assembly of Zero-Dimensional Organic Lead Bromide Hybrid with Efficient Blue Emission},
author = {Lin, Haoran and Zhou, Chenkun and Chaaban, Maya and Xu, Liang-Jin and Zhou, Yan and Neu, Jennifer and Worku, Michael and Berkwits, Ella and He, Qingquan and Lee, Sujin and Lin, Xinsong and Siegrist, Theo and Du, Mao-Hua and Ma, Biwu},
abstractNote = {Zero-dimensional (0D) organic metal halide hybrids are an emerging class of light emitting materials with exceptional photoluminescence quantum efficiencies (PLQEs), thanks to their perfect “host–guest” structures with light emitting metal halide species periodically “embedded” in a wide band gap organic cationic matrix through ionic bonds. However, achieving efficient blue emissions is challenging for this class of materials, as structural distortions of metal halides often lead to large Stokes shifts. Here we report a highly luminescent blue emitting 0D organic lead bromide, (C13H19N4)2PbBr4, with a peak emission of 460 nm (2.70 eV), a full width at half maximum (FWHM) of 66 nm (0.40 eV), a Stokes shift of 111 nm (0.85 eV), and a PLQE of ~40%. Single crystal structure analysis shows that individual PbBr42– species adopt a near-seesaw structure, which are coordinated to benzyl-hexamethylenetetrammonium (C13H19N4+) organic cations. The relatively small Stokes shift as compared to those of previously reported 0D organic metal halide hybrids are attributed to the low chemical reactivity of Pb 6s2 lone pairs and the rigid organic cationic matrix. Finally, (C13H19N4)2PbBr4 also shows exceptional stability in air with little-to-no change of properties for more than a year in ambient conditions.},
doi = {10.1021/acsmaterialslett.9b00333},
journal = {ACS Materials Letters},
number = 6,
volume = 1,
place = {United States},
year = {Mon Oct 21 00:00:00 EDT 2019},
month = {Mon Oct 21 00:00:00 EDT 2019}
}
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Figure 1: (a) Single crystal structure of (C13H19N4)2PbBr4 (red: lead atoms; green: bromine atoms; blue: nitrogen atoms; white: carbon atoms; blue polyhedron: PbBr4 seesaws; hydrogen atoms were hidden for clarity). (b) Monoclinic unit cell of (C13H19N4)2PbBr4. (c) Structure of an individual PbBr42- seesaw anion. (d) Structure of an individual C13H19N4+more »
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Microscopic origin of multiple exciton emission in low-dimensional lead halide perovskites
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