Eu 2+ –Eu 3+ valence transition in double, Eu-, and Na-doped PbSe from transport, magnetic, and electronic structure studies

Wiendlocha, Bartlomiej; Kim, SunPhil; Lee, Yeseul; He, Bin; Lehr, Gloria; Kanatzidis, Mercouri G.; Morelli, Donald T.; Heremans, Joseph P.

doi:10.1039/c7cp00358g

Title: Eu ²⁺ –Eu ³⁺ valence transition in double, Eu-, and Na-doped PbSe from transport, magnetic, and electronic structure studies

Journal Article · Mon Mar 27 00:00:00 EDT 2017 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c7cp00358g· OSTI ID:1425681

^[1]; Kim, SunPhil ^[2]; Lee, Yeseul ^[3]; He, Bin ^[2]; Lehr, Gloria ^[4]; Kanatzidis, Mercouri G. ^[3]; Morelli, Donald T. ^[4]; Heremans, Joseph P. ^[5]

AGH Univ. of Science and Technology, Krakow (Poland). Faculty of Physics and Applied Computer Science; The Ohio State Univ., Columbus, OH (United States). Dept of Mechanical & Aerospace Engineering
The Ohio State Univ., Columbus, OH (United States). Dept of Mechanical & Aerospace Engineering
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Michigan State Univ., East Lansing, MI (United States). Dept. of Chemical Engineering and Materials Science
The Ohio State Univ., Columbus, OH (United States). Dept of Mechanical & Aerospace Engineering, and Dept. of Physics

The Eu atoms in Pb_1-xEu_xSe have long been assumed to be divalent. We show that p-type doping of this magnetic semiconductor alloy with Na can modify the effective Eu valence: a mixed, Eu²⁺–Eu³⁺ state appears in Pb_1-x-yEu_xNa_ySe at particular values of y. Magnetization, carrier concentration, resistivity, and thermopower of Pb_1-x-yEu_xNa_ySe are reported for a number of samples with different x and y. A pronounced increase in thermopower at a given carrier concentration was identified and attributed to the presence of enhanced ionized impurity scattering. A strong decrease in the hole concentration is observed in Pb1-yNaySe when Eu is added to the system, which we attribute to a Eu²⁺–Eu³⁺ self-ionization process. This is evidenced by magnetization measurements, which reveal a significant reduction of the magnetic moment of Pb_1-xEu_xSe upon alloying with Na. Further, a deviation of magnetization from a purely paramagnetic state, described by a Brillouin function, identifies antiferromagnetic interactions between the nearest-neighbor Eu atoms: a value of J_ex/k_B = -0.35 K was found for the exchange coupling parameter. The conclusion of a Eu²⁺–Eu³⁺ self-ionization process being in effect is supported further by the electronic structure calculations, which show that an instability of the 4f⁷ configuration of the Eu²⁺ ion appears with Na doping. In conclusion, schematically, it was found that the Eu 4f levels form states near enough to the Fermi energy that hole doping can lower the Fermi energy and trigger a reconfiguration of a 4f electronic shell.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC); Michigan State Univ., East Lansing, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Polish National Science Centre (NCN)

Grant/Contract Number:: SC0001054; W911NF-14-1-0016; 1433467

OSTI ID:: 1425681

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 19, Issue 14; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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