<p>This study investigates the structural and magnetic tunability of Co–Cu ferrite nanoparticles via dual-site substitution of Cd<sup>2+</sup> at both Co<sup>2+</sup> and Cu<sup>2+</sup> lattice sites in the Co<sub>0.5</sub>Cu<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub> spinel lattice. Nanoparticles with the nominal composition Co<sub>0.5−x</sub>Cu<sub>0.5−x</sub>Cd<sub>2x</sub>Fe<sub>2</sub>O<sub>4</sub> (x = 0.00, 0.01, 0.02, 0.04, 0.06) were synthesized using an efficient co-precipitation method. The large ionic radius of Cd<sup>2+</sup> promotes its occupation of tetrahedral sites, which disrupts the magnetocrystalline anisotropy associated with Co<sup>2+</sup> and the Jahn–Teller distortions associated with Cu<sup>2+</sup>, leading to cation redistribution, modifications in superexchange interactions, and potentially the initiation of spin canting. Compared to single-site doping, this dual-site substitution introduces greater structural and magnetic complexity, offering a promising approach for multifunctional ferrite design. X-ray diffraction (XRD) confirmed a predominant face-centered cubic spinel phase with Co<sub>0.5</sub>Cu<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub> as the primary phase and a minor hematite (Fe<sub>2</sub>O<sub>3</sub>) secondary phase. Increasing Cd<sup>2+</sup> content induced a systematic lattice parameter expansion and crystallite size reduction (from 15.47&#xa0;nm to 12.11&#xa0;nm), indicating lattice distortion due to ionic substitution. TEM analysis showed quasi-spherical, slightly agglomerated nanoparticles with sizes decreasing from 15.47&#xa0;nm to 12.11&#xa0;nm as x increased from 0.00 to 0.06. HRTEM confirmed the material’s polycrystalline nature through observed (220) and (311) lattice fringes. FTIR spectra displayed two characteristic absorption bands 510–580&#xa0;cm<sup>−1</sup> and 400–450&#xa0;cm<sup>−1</sup>) confirming spinel formation, while Raman spectroscopy revealed a blue shift in the <InlineEquation ID="IEq1"> <EquationSource Format="TEX">\(\:{A}_{1g}\)</EquationSource> </InlineEquation>mode, associated with Fe<sup>3+</sup> migration towards tetrahedral sites. Additionally, XPS analysis confirmed the oxidation states of the constituent elements in the samples as Co<sup>2+</sup>, Cu<sup>2+</sup>, Fe<sup>3+</sup>, Cd<sup>2+</sup>and O<sup>2−</sup>. Vibrating sample magnetometry (VSM) measurements showed ferromagnetic hysteresis loops with a non-linear variation of saturation magnetization (<InlineEquation ID="IEq2"> <EquationSource Format="TEX">\(\:{M}_{s}\)</EquationSource> </InlineEquation>) and a significant reduction in coercivity (<InlineEquation ID="IEq3"> <EquationSource Format="TEX">\(\:{H}_{c}\)</EquationSource> </InlineEquation>) from 851.98 G to 306.06 G, reflecting progressive magnetic softening with Cd²⁺ incorporation. Complementary, ESR analysis showed asymmetric resonance line shapes, a downshift in <InlineEquation ID="IEq4"> <EquationSource Format="TEX">\(\:{H}_{r}\)</EquationSource> </InlineEquation>, and an enhancement in the Landé <InlineEquation ID="IEq5"> <EquationSource Format="TEX">\(\:g\)</EquationSource> </InlineEquation> -factor, which was consistent with modifications in the local magnetic environment. These tunable structural and magnetic properties highlight the potential of Cd-substituted Co–Cu ferrites for applications in high-frequency electronics and EMI shielding.</p>

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Structural and magnetic tailoring of Co-Cu ferrite nanoparticles via Cd2+ substitution: a multi-characterization approach

  • D. El-Said Bakeer,
  • M. Y. El Sayed,
  • E. M. Abdallah,
  • R. Awad,
  • S. G. Elsharkawy

摘要

This study investigates the structural and magnetic tunability of Co–Cu ferrite nanoparticles via dual-site substitution of Cd2+ at both Co2+ and Cu2+ lattice sites in the Co0.5Cu0.5Fe2O4 spinel lattice. Nanoparticles with the nominal composition Co0.5−xCu0.5−xCd2xFe2O4 (x = 0.00, 0.01, 0.02, 0.04, 0.06) were synthesized using an efficient co-precipitation method. The large ionic radius of Cd2+ promotes its occupation of tetrahedral sites, which disrupts the magnetocrystalline anisotropy associated with Co2+ and the Jahn–Teller distortions associated with Cu2+, leading to cation redistribution, modifications in superexchange interactions, and potentially the initiation of spin canting. Compared to single-site doping, this dual-site substitution introduces greater structural and magnetic complexity, offering a promising approach for multifunctional ferrite design. X-ray diffraction (XRD) confirmed a predominant face-centered cubic spinel phase with Co0.5Cu0.5Fe2O4 as the primary phase and a minor hematite (Fe2O3) secondary phase. Increasing Cd2+ content induced a systematic lattice parameter expansion and crystallite size reduction (from 15.47 nm to 12.11 nm), indicating lattice distortion due to ionic substitution. TEM analysis showed quasi-spherical, slightly agglomerated nanoparticles with sizes decreasing from 15.47 nm to 12.11 nm as x increased from 0.00 to 0.06. HRTEM confirmed the material’s polycrystalline nature through observed (220) and (311) lattice fringes. FTIR spectra displayed two characteristic absorption bands 510–580 cm−1 and 400–450 cm−1) confirming spinel formation, while Raman spectroscopy revealed a blue shift in the \(\:{A}_{1g}\) mode, associated with Fe3+ migration towards tetrahedral sites. Additionally, XPS analysis confirmed the oxidation states of the constituent elements in the samples as Co2+, Cu2+, Fe3+, Cd2+and O2−. Vibrating sample magnetometry (VSM) measurements showed ferromagnetic hysteresis loops with a non-linear variation of saturation magnetization ( \(\:{M}_{s}\) ) and a significant reduction in coercivity ( \(\:{H}_{c}\) ) from 851.98 G to 306.06 G, reflecting progressive magnetic softening with Cd²⁺ incorporation. Complementary, ESR analysis showed asymmetric resonance line shapes, a downshift in \(\:{H}_{r}\) , and an enhancement in the Landé \(\:g\) -factor, which was consistent with modifications in the local magnetic environment. These tunable structural and magnetic properties highlight the potential of Cd-substituted Co–Cu ferrites for applications in high-frequency electronics and EMI shielding.