Photoluminescence properties of Ce3+/Mn2+ doped calcium zirconium silicate phosphors with energy transfer for white LEDs

A series of Ce³⁺ doped and Ce³⁺/Mn²⁺ co-doped calcium zirconium silicate CaZrSi₂O₇ (CZS) phosphors have been synthesized via conventional high temperature solid state reactions. The luminescence properties, energy transfer between Ce³⁺ and Mn²⁺ have been investigated systematically. Under 320 nm excitation, the phosphor CZS: 0.05Ce³⁺ exhibit strong blue emission ranging from 330 nm to 500 nm, attributed to the spin-allowed 5d-4f transitions of Ce³⁺ ions. There are two different emission centers of Ce³⁺ ions, Ce³⁺(I) and Ce³⁺(II). The emission spectra of Ce³⁺, Mn²⁺ co-doped phosphors shows a broad emission around 550 nm corresponding to the ⁴T₁(⁴G)-⁶A₁(⁶S) spin-forbidden transition of Mn²⁺. The energy transfer between Ce³⁺ and Mn²⁺ is detected and the transfer efficiency of Ce³⁺(II) to Mn²⁺ is faster than that of Ce³⁺(I) to Mn²⁺. The resonant type is identified via dipole-dipole mechanism. Additionally, a blue-shift emission of Ce³⁺ and a red-shift emission of Mn²⁺ have been observed following the increase of Mn²⁺ content in relation to the energy transfer. Thermal quenching has been investigated and the emission spectra show a blue-shift with the temperature increases, which have been discussed in details. CZS: 0.05Ce³⁺, yMn²⁺ phosphors can be tuned from blue to white and even to yellow by adjusting the Mn²⁺ content. All the results indicate that CZS: Ce³⁺, Mn²⁺ phosphor have a potential application for near-UV LEDs.