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 journalArticle

Abstract

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 languageEnglish (US)
Pages (from-to)17421-17430
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number43
DOIs
StatePublished - Oct 30 2019

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Antiferromagnetism
Semiconductors
Photoluminescence
Semiconductor materials
Electron energy levels
Energy gap
Magnetoelectronics
Synchrotrons
Transition Temperature
Energy Transfer
Synchrotron radiation
Excited states
Optoelectronic devices
Energy transfer
Heating
Superconducting transition temperature
Anions
Cations
Negative ions
Positive ions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 43. pp. 17421-17430.
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abstract = "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.",
author = "Haijie Chen and Rebecca Mcclain and Jiangang He and Chi Zhang and Olding, {Jack N.} and {Dos Reis}, Roberto and Bao, {Jin Ke} and Ido Hadar and Ioannis Spanopoulos and Malliakas, {Christos D.} and Yihui He and Chung, {Duck Young} and Kwok, {Wai Kwong} and Weiss, {Emily A.} and Dravid, {Vinayak P.} and Christopher Wolverton and Kanatzidis, {Mercouri G.}",
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Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence. / 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.

In: Journal of the American Chemical Society, Vol. 141, No. 43, 30.10.2019, p. 17421-17430.

Research output: Contribution to journalArticle

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T1 - Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence

AU - Chen, Haijie

AU - Mcclain, Rebecca

AU - He, Jiangang

AU - Zhang, Chi

AU - Olding, Jack N.

AU - Dos Reis, Roberto

AU - Bao, Jin Ke

AU - Hadar, Ido

AU - Spanopoulos, Ioannis

AU - Malliakas, Christos D.

AU - He, Yihui

AU - Chung, Duck Young

AU - Kwok, Wai Kwong

AU - Weiss, Emily A.

AU - Dravid, Vinayak P.

AU - Wolverton, Christopher

AU - Kanatzidis, Mercouri G.

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Y1 - 2019/10/30

N2 - 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.

AB - 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.

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