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Title: Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence

Abstract

Semiconductors possessing both magnetic and optoelectronic properties are rare and promise applications in opto-spintronics. In this work, we report the mixed-anion semiconductor BaFMn0.5Te with a band gap of 1.76 eV and a work function of 5.08 eV, harboring both antiferromagnetism (AFM) and strong red photoluminescence (PL). The synthesis of BaFMn0.5Te in quantitative yield was accomplished using the "panoramic synthesis" technique and synchrotron radiation to obtain the full reaction map, from which we determined that the compound forms upon heating at 850 degrees C via an intermediate unknown phase. The structure refinement required the use of a (3+1)-dimensional superspace group Cmme(alpha 01/2)0ss. The material crystallizes into a ZrCuSiAs-like structure with alternating [BaF]+ and [Mn0.5Te]- layers and has a commensurately modulated structure with the q-vector of 1/6a* + 1/6b* + 1/2c* at room temperature arising from the unique ordering pattern of Mn2+ cations. Long-range AFM order emerges below 90 K, with two-dimensional short-range AFM correlations above the transition temperature. First-principles calculations suggest that BaFMn0.5Te is an indirect band gap semiconductor with the gap opening between Te 5p and Mn 3d orbitals, and the magnetic interactions between nearest-neighbor Mn2+ atoms are antiferromagnetic. Steady-state PL spectra show a broad strong emission centered at similarmore » to 700 nm, which we believe originates from the energy manifolds of the modulated Mn2+ sublattice and its defects. Time-resolved PL measurements reveal an increase in excited-state lifetimes with longer probe wavelengths, from 93 ns (at 650 nm) to 345 ns (at 800 nm), and a delayed growth (6.5 ± 0.3 ns) in the kinetics at 800 nm with a concomitant decay (4.1 ± 0.1 ns) at 675 nm. Together, these observations predict that there are multiple emissive states, with higher energy states populating lower energy states by energy transfer.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF)
OSTI Identifier:
1578051
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 43; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; panoramic synthesis; modulated structure; photoluminescence; magnetism

Citation Formats

Chen, Haijie, McClain, Rebecca, He, Jiangang, Zhang, Chi, Olding, Jack N., dos Reis, Roberto, Bao, Jin-Ke, Hadar, Ido, Spanopoulos, Ioannis, Malliakas, Christos D., He, Yihui, Chung, Duck Young, Kwok, Wai-Kwong, Weiss, Emily A., Dravid, Vinayak P., Wolverton, Christopher, and Kanatzidis, Mercouri G. Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence. United States: N. p., 2019. Web. doi:10.1021/jacs.9b09382.
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Chen, Haijie, McClain, Rebecca, He, Jiangang, Zhang, Chi, Olding, Jack N., dos Reis, Roberto, Bao, Jin-Ke, Hadar, Ido, Spanopoulos, Ioannis, Malliakas, Christos D., He, Yihui, Chung, Duck Young, Kwok, Wai-Kwong, Weiss, Emily A., Dravid, Vinayak P., Wolverton, Christopher, & Kanatzidis, Mercouri G. Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence. United States. https://doi.org/10.1021/jacs.9b09382
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Chen, Haijie, McClain, Rebecca, He, Jiangang, Zhang, Chi, Olding, Jack N., dos Reis, Roberto, Bao, Jin-Ke, Hadar, Ido, Spanopoulos, Ioannis, Malliakas, Christos D., He, Yihui, Chung, Duck Young, Kwok, Wai-Kwong, Weiss, Emily A., Dravid, Vinayak P., Wolverton, Christopher, and Kanatzidis, Mercouri G. Mon . "Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence". United States. https://doi.org/10.1021/jacs.9b09382. https://www.osti.gov/servlets/purl/1578051.
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@article{osti_1578051,
title = {Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence},
author = {Chen, Haijie and McClain, Rebecca and He, Jiangang and Zhang, Chi and Olding, Jack N. and dos Reis, Roberto and Bao, Jin-Ke and Hadar, Ido and Spanopoulos, Ioannis and Malliakas, Christos D. and He, Yihui and Chung, Duck Young and Kwok, Wai-Kwong and Weiss, Emily A. and Dravid, Vinayak P. and Wolverton, Christopher and Kanatzidis, Mercouri G.},
abstractNote = {Semiconductors possessing both magnetic and optoelectronic properties are rare and promise applications in opto-spintronics. In this work, we report the mixed-anion semiconductor BaFMn0.5Te with a band gap of 1.76 eV and a work function of 5.08 eV, harboring both antiferromagnetism (AFM) and strong red photoluminescence (PL). The synthesis of BaFMn0.5Te in quantitative yield was accomplished using the "panoramic synthesis" technique and synchrotron radiation to obtain the full reaction map, from which we determined that the compound forms upon heating at 850 degrees C via an intermediate unknown phase. The structure refinement required the use of a (3+1)-dimensional superspace group Cmme(alpha 01/2)0ss. The material crystallizes into a ZrCuSiAs-like structure with alternating [BaF]+ and [Mn0.5Te]- layers and has a commensurately modulated structure with the q-vector of 1/6a* + 1/6b* + 1/2c* at room temperature arising from the unique ordering pattern of Mn2+ cations. Long-range AFM order emerges below 90 K, with two-dimensional short-range AFM correlations above the transition temperature. First-principles calculations suggest that BaFMn0.5Te is an indirect band gap semiconductor with the gap opening between Te 5p and Mn 3d orbitals, and the magnetic interactions between nearest-neighbor Mn2+ atoms are antiferromagnetic. Steady-state PL spectra show a broad strong emission centered at similar to 700 nm, which we believe originates from the energy manifolds of the modulated Mn2+ sublattice and its defects. Time-resolved PL measurements reveal an increase in excited-state lifetimes with longer probe wavelengths, from 93 ns (at 650 nm) to 345 ns (at 800 nm), and a delayed growth (6.5 ± 0.3 ns) in the kinetics at 800 nm with a concomitant decay (4.1 ± 0.1 ns) at 675 nm. Together, these observations predict that there are multiple emissive states, with higher energy states populating lower energy states by energy transfer.},
doi = {10.1021/jacs.9b09382},
journal = {Journal of the American Chemical Society},
number = 43,
volume = 141,
place = {United States},
year = {Mon Oct 07 00:00:00 EDT 2019},
month = {Mon Oct 07 00:00:00 EDT 2019}
}
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