Charge Transfer-Triggered Bi³⁺ Near-Infrared Emission in Y₂Ti₂O₇ for Dual-Mode Temperature Sensing

Trivalent bismuth is a popular main group ion showing versatile luminescent behaviors in a broad spectral range from ultraviolet to visible, but barely in the near-infrared (NIR) region. In this study, we have observed unexpected NIR emission at ∼744 nm in a Bi³⁺-doped pyrochlore, Y₂Ti₂O₇ (YTOB). Our first-principles electronic structure calculation and analysis of the Bi local structure via extended X-ray absorption fine structure indicate that only Bi³⁺ species appears in YTOB and it has a similar local environment to that of Y³⁺. The NIR emission is assigned to a Ti⁴⁺ → Bi³⁺ metal-to-metal charge transfer process. Moreover, we have demonstrated dual-mode luminescence thermometry based on the luminescence intensity ratio (LIR) and lifetime (τ) in 0.5% Bi³⁺ and 0.5% Pr³⁺ co-doped Y₂Ti₂O₇ (YTOB0.5P0.5). It exhibits high thermometric sensitivity simultaneously in the cryogenic temperature range from 78 to 298 K based on τ of the NIR emission of Bi³⁺ at 748 nm and in the temperature range of 278-378 K based on the LIR of Bi³⁺ to Pr³⁺ emissions (I₇₄₈/I₆₁₅). As a novel LIR-τ dual-mode thermometric material over a wide temperature range, the maximum relative sensitivities of the YTOB0.5P0.5 reach 3.53% K^-1 at 298 K from the τ mode and 3.52% K^-1 at 318 K based on the LIR mode. The dual-mode luminescence thermometry with high responsivity from our Bi³⁺-based pyrochlore Y₂Ti₂O₇ phosphor opens a new avenue for more luminescent materials toward multi-mode thermometry applied in complex temperature-sensing conditions.