Abstract
Copper(I) iodide hybrids are of interest for next-generation lighting technologies because of their efficient luminescence in the absence of rare-earth elements. Here, we report 10 structurally diverse hybrid copper(I) iodides that emit in the green-red region with quantum yields reaching 67%. The compounds display a diversity of structures including ones with one-dimensional (1D) Cu-1 chains, Cu2I2 rhomboid dimers, and structures with two different arrangements of Cu4I4 tetramers. The compounds with Cu2I2 rhomboid dimers or Cu4I4 cubane tetramers have higher photoluminescence quantum yields than those with Cu-I 1D chains and octahedral Cu4I4 tetramers, owing to the optimal degree of condensation of the inorganic motifs, which suppresses nonradiative processes. Electronic structure calculations on these compounds point out the critical influence of the inorganic motif and organic ligand on the nature of the band gaps and thus the excitation characteristics. Temperature-dependent photoluminescence spectra are presented to better understand the nature of luminescence in compounds with different inorganic motifs. The emerging understanding of composition-structure-property correlations in this family provides inspiration for the rational design of hybrid phosphors for general lighting applications.
Original language | English (US) |
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Pages (from-to) | 3206-3216 |
Number of pages | 11 |
Journal | Chemistry of Materials |
Volume | 34 |
Issue number | 7 |
DOIs | |
State | Published - Apr 12 2022 |
Funding
This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under the grant DE-SC-0012541. We thank Anthony K. Cheetham for useful discussions. S.W. thanks the China Scholarship Council for a State Scholarship Fund. P.V. thanks the Science and Engineering Research Board (SERB) of the Govt. of India for a Ramanujan Fellowship (Award No. RJF/2020/000106) and the Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore for financial support and research infrastructure. This work made use of the facilities of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara supported by the National Science Foundation (DMR 1720256). SMLT has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE- 1650114. S.P. has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE-1842165 and the Ryan Fellowship at Northwestern University. The ultrafast laser system used for the PLLT measurements was funded by DURIP ARO grant 66886LSRIP. This work was performed in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under the grant DE-SC-0012541. We thank Anthony K. Cheetham for useful discussions. S.W. thanks the China Scholarship Council for a State Scholarship Fund. P.V. thanks the Science and Engineering Research Board (SERB) of the Govt. of India for a Ramanujan Fellowship (Award No. RJF/2020/000106) and the Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore for financial support and research infrastructure. This work made use of the facilities of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara supported by the National Science Foundation (DMR 1720256). SMLT has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE- 1650114. S.P. has been supported by the NSF Graduate Research Fellowship Program under Grant No. DGE-1842165 and the Ryan Fellowship at Northwestern University. The ultrafast laser system used for the PLLT measurements was funded by DURIP ARO grant 66886LSRIP. This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
ASJC Scopus subject areas
- General Chemistry
- General Chemical Engineering
- Materials Chemistry
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CCDC 2123474: Experimental Crystal Structure Determination
Wang, S. (Contributor), Morgan, E. E. (Contributor), Panuganti, S. (Contributor), Mao, L. (Contributor), Vishnoi, P. (Contributor), Wu, G. (Contributor), Liu, Q. (Contributor), Kanatzidis, M. G. (Contributor), Schaller, R. D. (Contributor) & Seshadri, R. (Contributor), Cambridge Crystallographic Data Centre, 2022
DOI: 10.5517/ccdc.csd.cc298n5f, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc298n5f&sid=DataCite
Dataset
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CCDC 2123475: Experimental Crystal Structure Determination
Wang, S. (Contributor), Morgan, E. E. (Contributor), Panuganti, S. (Contributor), Mao, L. (Contributor), Vishnoi, P. (Contributor), Wu, G. (Contributor), Liu, Q. (Contributor), Kanatzidis, M. G. (Contributor), Schaller, R. D. (Contributor) & Seshadri, R. (Contributor), Cambridge Crystallographic Data Centre, 2022
DOI: 10.5517/ccdc.csd.cc298n6g, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc298n6g&sid=DataCite
Dataset
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CCDC 2123481: Experimental Crystal Structure Determination
Wang, S. (Contributor), Morgan, E. E. (Contributor), Panuganti, S. (Contributor), Mao, L. (Contributor), Vishnoi, P. (Contributor), Wu, G. (Contributor), Liu, Q. (Contributor), Kanatzidis, M. G. (Contributor), Schaller, R. D. (Contributor) & Seshadri, R. (Contributor), Cambridge Crystallographic Data Centre, 2022
DOI: 10.5517/ccdc.csd.cc298ndn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc298ndn&sid=DataCite
Dataset