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A. Sieradzki

Publications and source records attributed to A. Sieradzki.

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Ionic-Radius Mismatch as a Structural Lever for Tuning Phase Transitions and Luminescent Thermometry

The widespread implementation of luminescence thermometers requires a comprehensive understanding of the structural factors governing their thermometric performance. Establishing such structure-property relationships is essential for the rational design of sensing materials with application-tailored characteristics. This is particularly relevant for phase-transition-based luminescence thermometers, which offer exceptionally high relative sensitivities. The systematic analysis of K3Lu(PO4)2:Eu3+ demonstrates that introducing co-dopant ions with a controlled ionic-radius mismatch provides an effective strategy for tailoring phase-transition characteristics. This approach enables both the phase-transition temperature and thermal operating range to be controlled. Specifically, the transition temperature shifts from 210 K for K3Lu(PO4)2:Eu3+ to 310 K for K3Lu(PO4)2:Eu3+,10%La3+, while the operating range broadens from 30 to 60 K. Importantly, linear correlations between the ionic-radius mismatch parameter, Ω, and the phase-transition temperature, enthalpy, and entropy provide a quantitative framework for controlling the thermodynamics of the transition through compositional engineering. Beyond luminescence thermometry, these relationships establish a general strategy for designing materials exhibiting first-order phase transitions with tailored thermodynamic characteristics, opening opportunities for their optimization across a broad range of functional applications.

cond-mat.mtrl-sci

Second-Coordination-Sphere Cation Substitution as a Tool for Controlling Phase Transitions and Performance of the Luminescence Thermometry

Despite the exceptionally high relative sensitivities achieved by luminescent thermometers based on first-order structural phase transitions, their principal limitation lies in the inherently narrow thermal operating range associated with the transition temperature. In this work, we demonstrate that partial substitution of Li+ by Na+ ions in the second coordination sphere of Eu3+ ions in LiYO2 enables a substantial shift of the phase transition temperature, thereby allowing controlled optimization of the thermometric performance. This approach represents a significantly more cost-effective and efficient strategy for tuning the phase transition temperature compared with the previously proposed substitution of Y3+ by other lanthanide ions. Importantly, we show that lowering the transition temperature through Na+ incorporation simultaneously introduces static compositional disorder and local lattice strain. As a consequence, the enthalpy difference between the competing structural phases decreases, and the cooperativity of the lattice distortion is reduced, indicating a gradual weakening of the first-order character of the phase transition. Our results demonstrate that such structural modifications, while effective in shifting the transition temperature, inevitably lead to a reduction in the relative sensitivity of phase-transition-based luminescent thermometers.

cond-mat.mtrl-sci