Synthesis and Study of Fe-Doped Bi2S3 Semimagnetic Nanocrystals Embedded in a Glass Matrix

• Autor(a) principal: Silva, Ricardo Souza
• Data de Publicação: 2017
• Outros Autores: Mikhail, Hanna Degani, Guimaraes, Eder Vinícius, Gonçalves, Elis Regina, Cano, Nilo Francisco [UNIFESP], Dantas, Noelio Oliveira
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Institucional da UNIFESP
• Texto Completo: https://dx.doi.org/10.3390/molecules22071142; https://repositorio.unifesp.br/handle/11600/53552
• topic: Fe-doped bismuth sulphide; Nanocrystal synthesis; Density functional theory

Iron-doped bismuth sulphide (Bi2-xFexS3) nanocrystals have been successfully synthesized in a glass matrix using the fusion method. Transmission electron microscopy images and energy dispersive spectroscopy data clearly show that nanocrystals are formed with an average diameter of 7-9 nm, depending on the thermic treatment time, and contain Fe in their chemical composition. Magnetic force microscopy measurements show magnetic phase contrast patterns, providing further evidence of Fe incorporation in the nanocrystal structure. The electron paramagnetic resonance spectra displayed Fe3+ typical characteristics, with spin of 5/2 in the 3d(5) electronic state, thereby confirming the expected trivalent state of Fe ions in the Bi2S3 host structure. Results from the spin polarized density functional theory simulations, for the bulk Fe-doped Bi2S3 counterpart, corroborate the experimental fact that the volume of the unit cell decreases with Fe substitutionally doping at Bi1 and Bi2 sites. The Bader charge analysis indicated a pseudo valency charge of 1.322| e | on Fe-Bi1 and 1.306 | e | on Fe-Bi2 ions, and a spin contribution for the magnetic moment of 5.0 mu(B) per unit cell containing one Fe atom. Electronic band structures showed that the (indirect) band gap changes from 1.17 eV for Bi2S3 bulk to 0.71 eV (0.74 eV) for Bi2S3: Fe-Bi1 (Bi2S3: Fe-Bi2). These results are compatible with the 3d(5) high-spin state of Fe3+, and are in agreement with the experimental results, within the density functional theory accuracy.