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Strong f-f excitation and bright red emission in Cd4Gd1-xEuxO(BO3)3 (0 ≤ x ≤ 1): near-UV LED pumped red phosphors with low thermal quenching.

Searching efficient red phosphors under near UV or blue light excitation is practically important to improve the current white light emitting diodes (WLEDs). Eu2+- and Mn4+-based red phosphors have been extensively studied, here we proposed that Eu3+ is also a promising activator when it resides on a noncentrosymmetric coordination site. We proved that Cd4GdO(BO3)3 is a good host, which has a significantly distorted coordination for Eu3+. A careful crystallographic study was performed on the solid solutions of Cd4Gd1-xEuxO(BO3)3 (0 ≤ x ≤ 1) by Rietveld refinements. The as-doped Eu3+ cations locate at the Gd3+ site and are well separated by CdO8, CdO6 and BO3 groups, thus only a slight concentration quenching was observed at ~80 atom% Eu3+. Most importantly, the parity-forbidden law of 4f-4f transitions for Eu3+ are severely depressed, thus the absorptions at ~393 and ~465 nm are remarkable. Cd4Gd0.2Eu0.8O(BO3)3 can be pumped by a 395 nm LED chip to give a bright red emission, and when mixed with other commercial blue and green phosphors, it can emit the proper white light (0.3657, 0.3613) with a suitable Ra ~ 87 and correlated colour temperature ~4326 K. In-situ photoluminescence study indicated the low thermal quenching of these borate phosphors, especially under 465 nm excitation. Our case proves the practicability to develop near UV excited red phosphors in rare-earth-containing borates.

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