Vacancy-Enhanced Self-Reduction of Eu in Pyrophosphate Phosphor

Abstract

The self-reduction mechanism in pyrophosphate phosphors is currently explained through nonequivalent substitution for charge compensation. Nevertheless, the impact of oxygen vacancies on the self-reduction enhancement requires further investigation. Herein, heterovalent Ba1–x Zn1–y P2O7:xEu2+/3+, yMg phosphors with rigid structures were prepared through conventional solid-phase technology in air. The cation substitution strategy leads to different chemistry electronegativity and adjustable crystal field environments and creates vacancy defects. Crystal structure and component analysis indicate the gradual phase segregation change from BaZnP2O7 to BaMgP2O7 with increasing Mg2+ content. The CIE coordinates that are tuned from (0.514, 0.334) to (0.326, 0.152) and realize color-tunable emission from red-orange to blue-violet can be used as multicolor functional materials. Besides, the phosphor demonstrates its maximum S a of 0.4725% K–1 (498 K) and S r of 1.376% K–1 (423 K). These results demonstrate that the phosphors have the potential for contactless optical temperature measurement and anticounterfeiting. This work not only investigates the self-reduction of the Eu3+ → Eu2+ phenomenon but also provides a supplementary explanation and data support to complete the effect of the oxygen vacancy on self-reduction.

Utilizing diametrically opposite thermal quenching luminescence to achieve highly sensitive temperature measurement and anti-counterfeiting

“…Nevertheless, the Ga 3+ ions reside in a tetrahedral position. To investigate the occupancy situation of Eu 2+ , Eu 3+ and Tb 3+ ions, the ionic radius percentage discrepancy ( D r ) between the doped ions and the possible occupied ions (Ca 2+ , Y 3+ , and Ga 3+ ) is calculated based on the following formula: 28 where R m is the cation radius, R d is the dopant ion radius, and CN is the cation coordination number. Table S2† provides the corresponding calculation results.…”