Tunable Photoluminescence and Energy Transfer Efficiency in β‑Ca3(PO4)2‑Ca9La(PO4)7:Eu2+, Mn2+ Solid Solution Phosphors Introduced by Emptying Site and Structural Confinement Effect for Solid-State Lighting Application

Full visible emission achieved by a single-phased system is of great interest to researchers for the development of high-quality solid-state lighting devices. Herein, novel Eu2+ and Mn2+ co-doped (1 – x)­β-Ca3(PO4)2-xCa9La­(PO4)7 solid solution phosphors are designed to realize single-phased white light emission. The effects of variational x on lattice structure, color-tunable emission, thermal stability, and energy-transfer efficiency from Eu2+ to Mn2+ are systematically investigated. Tunable color emissions are achieved by manipulating the redistributions of Eu2+ ions among the different cationic sites under the influence of generated empty site in the M(4) site. Meanwhile, the changes of critical distances among the Eu2+ and Mn2+ caused by the variational x results in the changes of energy-transfer efficiency from different Eu2+ luminescent centers to Mn2+ due to the existence of structural confinement effect. The calculated results indicate that Eu1–Mn and Eu2–Mn possess higher energy-transfer efficiencies than other Eu–Mn pairs. Under the combined influence of the two effects, single-phased full visible white emission covering from 400 to 700 nm has been realized via the adjustment of solid solution, which makes the fabricated white-light-emitting diode (WLED) possess high color-rendering index (86.9) and R9 (87.2) as well as low correlated color temperature (3947 K). The results show that the 0.2β-Ca3(PO4)2-0.8Ca9La­(PO4)7:0.01Eu2+, 0.20Mn2+ could act as a promising phosphor for single-phased WLEDs. This work will open up a new avenue for tuning the multiple activator sites and energy-transfer efficiencies simultaneously to realize single-phased full visible white emission.