Applied Sciences, Vol. 16, Pages 786: Transition Metal-Doped ZnO and ZrO2 Nanocrystals: Correlations Between Structure, Magnetism, and Vibrational Properties—A Review

Applied Sciences doi: 10.3390/app16020786

Authors:
Izabela Kuryliszyn-Kudelska
Witold Daniel Dobrowolski

Transition metal (TM)-doped zinc oxide (ZnO) and zirconium dioxide (ZrO2) nanocrystals exhibit complex correlations between crystal structure, defect chemistry, vibrational properties, and magnetic behavior that are strongly governed by synthesis route and dopant incorporation mechanisms. This review critically summarizes recent progress on Fe-, Mn-, and Co-doped ZnO and ZrO2 nanocrystals synthesized by wet chemical, hydrothermal, and microwave-assisted hydrothermal methods, with emphasis on synthesis-driven phase evolution and apparent solubility limits. ZnO and ZrO2 are treated as complementary host lattices: ZnO is a semiconducting, piezoelectric oxide with narrow solubility limits for most 3d dopants, while ZrO2 is a dielectric, polymorphic oxide in which transition metal doping may stabilize tetragonal or cubic phases. Structural and microstructural studies using X-ray diffraction, electron microscopy, Raman spectroscopy, and Mössbauer spectroscopy demonstrate that at low dopant concentrations, TM ions may be partially incorporated into the host lattice, giving rise to diluted or defect-mediated magnetic behavior. When solubility limits are exceeded, nanoscopic secondary oxide phases emerge, leading to superparamagnetic, ferrimagnetic, or spin-glass-like responses. Magnetic measurements, including DC magnetization and AC susceptibility, reveal a continuous evolution from paramagnetism in lightly doped samples to dynamic magnetic states characteristic of nanoscale magnetic entities. Vibrational spectroscopy highlights phonon confinement, surface optical phonons, and disorder-activated modes that sensitively reflect nanocrystal size, lattice strain, and defect populations, and often correlate with magnetic dynamics. Rather than classifying these materials as diluted magnetic semiconductors, this review adopts a synthesis-driven and correlation-based framework that links dopant incorporation, local structural disorder, vibrational fingerprints, and magnetic response. By emphasizing multi-technique characterization strategies required to distinguish intrinsic from extrinsic magnetic contributions, this review provides practical guidelines for interpreting magnetism in TM-doped oxide nanocrystals and outlines implications for applications in photocatalysis, sensing, biomedicine, and electromagnetic interference (EMI) shielding.

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