Synthesis of Mixed‐Valent Lanthanide Sulfide Nanoparticles

• Published in: Angewandte Chemie International Edition 2021-10, Vol.60 (43), p.23134-23141
• Main Authors: Glaser, Priscilla, Stewart, Orlando, Atif, Rida, Asuigui, Dane Romar C., Swanson, Joel, Biacchi, Adam J., Hight Walker, Angela R., Morrison, Gregory, Loye, Hans‐Conrad, Stoll, Sarah L.
• Format: Article
• Language: English
• Subjects: Ferromagnetism; Halides; lanthanide chalcogenides; Magnetic permeability; Magnetic susceptibility; magnetism; Morphology; Nanoparticles; phase transformation; Photoelectrons; semiconductors; Sulfides; Synthesis; Transmission electron microscopy
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202108993

In targeting reduced valent lanthanide chalcogenides, we report the first nanoparticle synthesis of the mixed‐valent ferromagnets Eu3S4 and EuSm2S4. Using divalent lanthanide halides with bis(trimethylsilyl)sulfide and oleylamine, we prepared nanoparticles of EuS, Eu3S4, EuSm2S4, SmS1.9, and Sm3S4. All nanoparticle phases were identified using powder X‐ray diffraction, transmission electron microscopy was used to confirm morphology and nanoparticle size, and magnetic susceptibility measurements for determining the ordering temperatures and valence. The UV/Vis, Raman and X‐ray photoelectron spectroscopies for each phase were compared. Surprisingly, the phase is influenced by the halide and the reaction temperature, where EuCl2 formed EuS while EuI2 formed Eu3S4, highlighting the role of kinetics in phase stabilization. Interestingly, at lower temperatures EuI2 initially forms EuS, and converts over time to Eu3S4. Using divalent lanthanide halides with bis(trimethylsilyl)sulfide and oleylamine, the mixed‐valent ferromagnets Eu3S4 and EuSm2S4; and EuS, SmS1.9, and Sm3S4 were prepared. The phase is influenced by the halide and the reaction temperature, where EuCl2 formed EuS while EuI2 formed Eu3S4, highlighting the role of kinetics in phase stabilization. Interestingly, at lower temperatures EuI2 initially forms EuS, and converts over time to Eu3S4.