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

Haijie Chen, Rebecca Mcclain, Jiangang He, Chi Zhang, Jack N. Olding, Roberto Dos Reis, Jin Ke Bao, Ido Hadar, Ioannis Spanopoulos, Christos D. Malliakas, Yihui He, Duck Young Chung, Wai Kwong Kwok, Emily A. Weiss, Vinayak P. Dravid, Christopher Wolverton, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Semiconductors possessing both magnetic and optoelectronic properties are rare and promise applications in opto-spintronics. Here 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 °C via an intermediate unknown phase. The structure refinement required the use of a (3+1)-dimensional superspace group Cmme(α01/2)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 indicate 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 at700 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 suggest that there are multiple emissive states, with higher energy states populating lower energy states by energy transfer.

Original languageAmerican English
Pages (from-to)17421-17430
Number of pages10
JournalJournal of the American Chemical Society
Issue number43
StatePublished - 30 Oct 2019
Externally publishedYes

Bibliographical note

Funding Information:
This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE-AC02-06CH11357 at Argonne National Laboratory (materials synthesis, crystal growth, and magnetism studies), and by the National Science Foundation’s (NSF) MRSEC program (DMR-1720139) at the Materials Research Center of Northwestern University (panoramic in situ X-ray diffraction, XPS, UV/Vis spectroscopy, and single crystal X-ray crystallography). Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC0206CH11357. Use of the Center for Nanoscale Materials, an Office of Science user facility, was also supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC0206CH11357. SEM-EDS and TEM were performed by use of the EPIC, Keck-II, and/or SPID facility(ies) of Northwestern University’s NU ANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. PYSA measurements were carried out with equipment acquired by ONR grant N00014-18-1-2102. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231.

Publisher Copyright:
© 2019 American Chemical Society.


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