Al₂O₃:Cr³⁺ coatings were synthesized on tungsten substrates by plasma electrolytic oxidation in a phosphate-aluminate electrolyte containing dispersed Cr₂O₃ nanoparticles, and their structural, photoluminescent, and temperature-sensing properties were investigated. The coatings exhibited a typical porous PEO morphology with a uniform thickness of approximately 31 μm, and EDS analysis confirmed the incorporation of Cr species from the electrolyte, with Cr content increasing with the concentration of Cr₂O₃ particles. XRD analysis showed that the coatings were composed predominantly of α-Al₂O₃, with minor contributions from metastable γ-Al₂O₃, confirming that our previously established process for forming the thermodynamically stable α-Al₂O₃ phase directly on a non-aluminum substrate remains robust upon the introduction of dopant nanoparticles. The Al₂O₃:Cr³⁺ coatings displayed characteristic ruby-like photoluminescence, including broad excitation bands associated with the ⁴A₂⟶⁴T₁ and ⁴A₂⟶⁴T₂ transitions and sharp R-line emission arising from the spin-forbidden ²E⟶⁴A₂ transition. The strongest emission was obtained for coatings prepared with 0.05 g/L Cr₂O₃, while higher concentrations resulted in concentration quenching. Temperature-dependent photoluminescence revealed two complementary thermometric mechanisms: R-line spectral shifting and thermally induced redistribution between the ²E and ⁴T₂ emissions. The deconvolution-based intensity-ratio approach provided a stronger temperature response than simple spectral partitioning, demonstrating the potential of PEO-derived Al₂O₃:Cr³⁺ coatings on tungsten as robust luminescent temperature-sensing layers.

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