Mn4+/Eu3+ co-doped fluoride toward a blue light-excited optical fiber thermometer.

The ongoing development of ratiometric optical thermometry is mainly trapped in thermally coupled levels of rare-earth ions and inefficient ultraviolet excitation. Herein, a new-type multiple sharp line emitting, blue light-excited K2NaInF6:Mn4+, Eu3+ fluoride phosphor has been reported as a ratiometric thermometer. The f-f transition of Eu3+ paves a steady reference to a highly temperature sensitive Mn4+d-d transition and enables high relative sensitivity of 1.65% K-1 at 573 K. An optical fiber thermometry on a household oven with a relative standard deviation of 0.11% surpasses the standard of precision measurement, showing great potential in practical application. This discovery offers a highly sensitive neotype blue light-excitable ratiometric temperature sensor, that is Mn4+-doped fluoride, promoting practical applications of optical thermometry.

Stable Polyhedron-Cluster-Based Rigid Fluoride Framework toward Zero-Thermal-Quenching Near-Infrared Emission for Prolonged LED Applications.

Development of highly thermally stable broadband near-infrared (NIR) luminescence materials is crucial for advancing the prolonged stable application of smart NIR light sources. In this study, a zero-thermal-quenching and reversible temperature-dependent broadband NIR-emitting Cs2NaAl3F12:Cr3+ phosphor is demonstrated, benefiting from its stable polyhedron-cluster-building rigid structure. The excellent thermal stability of Cs2NaAl3F12:Cr3+ is rooted in its stable [Al6Na4F45] cluster building unit, which provides a rigid structure with a weak electron-phonon coupling effect and a wide band gap with a huge thermal activated barrier. Such characteristics are well revealed by multiple studies on crystal structure, electronic structure, Huang-Rhys factor S, configuration coordinate model, and Debye temperature. The incorporation of Li or K instead of Na weakens the luminescence thermal stability, directly proving the importance of the stable [Al6Na4F45] cluster for stable Cr3+ substitution and rigid structure construction. Furthermore, Cs2NaAl3F12:Cr3+ presents much superior thermal stability compared to traditional rigid garnet-type fluorides Na3X2Li3F12:Cr3+ (X = Al, Ga, In). A high-power NIR LED is presented, utilizing the high quantum efficiency (∼71%) and extremely thermally stable broadband NIR emission around 750 nm of Cs2NaAl3F12:Cr3+. It realizes clear vein and cartilage imaging in the human hand, demonstrating its potential in medical diagnosis applications. This result provides important insights for designing new-type rigid crystal structures using stable polyhedron clusters as basic units, advancing the development of highly thermally stable NIR-emitting phosphors.

Defect-related luminescence behavior of a Mn4+ non-equivalently doped fluoroantimonate red phosphor.

Non-equivalent or non-octahedral substitution is a crucial strategy to gain Mn4+-doped fluoride red phosphors with a short fluorescence lifetime, whereas the impact of their structural defects on the photoluminescence (PL) properties remains unrevealed. Here, a non-equivalently doped RbSbF6:Mn4+ (RSFM) with a high quantum efficiency of 88% and a thermal stability of 121% at 425 K is newly reported to probe the defect-related PL behavior. Formation energy calculations imply that an interstitial defect was formed to balance the charge and stabilize the crystal structure. Concentration-dependent decay studies reveal that Mn4+ emission is quenched mainly by energy transfer to a neighboring defect . The large ionic radius of Sb5+ and defect leading to a premature optimal doping (0.11 mol%) is demonstrated by the refined contrast of the crystal structure and substitution mode among various Mn4+-doped prototypes. A couple of medium 4T2 state energies and the energy difference between the Mn4+ level with the valence band maximum enable its superior thermal stability. A higher defect concentration slightly aggravates this thermal quenching. Using the RSFM red phosphor in a white light-emitting diode offers a wide-color-gamut of 121% NTSC for backlight displays. This work would provide a new perspective to understand the defect effect on the PL behavior of special Mn4+ asymmetrically doped fluorides.