Thermal Quenching Mechanism of Metal-Metal Charge Transfer State Transition Luminescence Based on Double-Band-Gap Modulation.

Abstract

Bi3+-related metal-to-metal charge transfer (MMCT) transition phosphors are expected to become a new class of solid-state luminescent materials due to their unique broadband long-wavelength emission; however, the main obstacle to their application is the thermal quenching effect. In this study, one novel thermal quenching mechanism of Bi3+-MMCT transition luminescence is proposed by introducing electron-transfer potential energy (ΔET). Y0.99V1-xPxO4:0.01Bi3+ (YV1-xPxO4:Bi3+) is used as the model; when the band gap of the activator Bi3+ increases from 3.44 to 3.76 eV and the band gap of the host YV1-xPxO4 widens from 2.75 to 3.16 eV, the electron-transfer potential energy (ΔET) decreases and the thermal quenching activation energy (ΔE) increases, which result in the relative emission intensity increasing from 0.06 to 0.64 at 303-523 K. Guided by density functional calculations, the thermal quenching mechanism of the Bi3+-MMCT state transition luminescence is revealed by the double-band-gap modulation model of the activator ion and the matrix. This study improves the thermal quenching theory of different types of Bi3+ transition luminescence and offers one neo-theory guidance for the contriving and researching of high-quality luminescence materials.