Pushing the Limit of Boltzmann Distribution in Cr³⁺-Doped CaHfO₃ for Cryogenic Thermometry

Luminescence Boltzmann thermometry is one of the most reliable techniques used to locally probe temperature in a contactless mode. However, to date, there is no report on cryogenic thermometers based on the highly sensitive and reliable Boltzmann-based ⁴T₂ → ⁴A₂/²E → ⁴A₂ emission ratio of Cr³⁺. On the basis of structural information of the local HfO₆ octahedral site we demonstrated the potential of the CaHfO₃:Cr³⁺ system by combining deep theoretical and experimental investigation. The material exhibits simultaneous emission from both the ²E and ⁴T₂ excited states, following the Boltzmann law in a cryogenic temperature range of 40-150 K. The promising thermometric performance corroborates the potential of CaHfO₃:Cr³⁺ as a Boltzmann cryothermometer, being characterized by a high relative sensitivity (∼ 2%·K^-1 at 40 K) and exceptional thermal resolution (0.045-0.77 K in the 40-150 K range). Moreover, by exploiting the flexibility of the ⁴T₂-²E energy gap controlled by the crystal field of the local octahedral site, the design proposed herein could be expanded to develop new Cr³⁺-doped cryogenic thermometers.