Equivalent chemical substitution in double–double perovskite-type ALaLiTeO₆:Mn⁴⁺ (A = Ba²⁺, Sr²⁺, Ca²⁺) phosphors enabling wide range crystal field strength regulation and efficient far-red emission

Abstract

Mn⁴⁺-activated phosphors have shown wide prospective applications in phosphor-converted white light-emitting diodes (pc-WLEDs) and pc-LEDs used in illumination and indoor plant cultivation, respectively. Recently, double perovskites A₂B'B''O₆ with a tunable crystal structure and versatile octahedral sites have been extensively studied as good host matrixes for Mn⁴⁺-emitters to realize tunable far-red emissions. Herein, a series of double-double perovskite-type ALaLiTeO₆:Mn⁴⁺ (A = Ba, Ba_0.5Sr_0.5, Sr, Sr_0.5Ca_0.5, Ca) phosphors were synthesized and structurally characterized, and the correlations between their structure and luminescence were also studied systematically. With a decrease of the A-cation size, an increased distortion in the average structure and a structure symmetry lowering (<i>I</i>2/<i>m</i> → <i>P</i>2₁/_n) were observed for ALaLiTeO₆:Mn⁴⁺. In contrast, on the local scale, the degree of (Li/Te)O₆-octahedral distortion is positively correlated with the Δ<i>IR</i> value, which is the ionic radius difference between A²⁺ and La³⁺. The local structural changes were found to be irrelevant to the significant improvements in photoluminescence properties. In combination with careful spectroscopic analysis, we deciphered that a decreased A-cation is in fact helpful for the enhancements in crystal field strength (<i>D</i>_q/<i>B</i> = 2.12-2.82) and Mn-O covalent bonding, thereby resulting in an improved quantum efficiency, a suppressed nonradiative transition, and a redshift in photoluminescence spectra. Amongst the ALaLiTeO₆:Mn⁴⁺ phosphor series, CaLaLiTeO₆:Mn⁴⁺ exhibits the highest external quantum efficiency of 70.1% and internal quantum efficiency of 96.4% and superior thermal stability (93.3%@423 K), making CaLaLiTeO₆:Mn⁴⁺ very promising as far-red phosphors for pc-LEDs. The findings of this work will serve as a new guide for rational design of high-performance Mn⁴⁺-activated double-double perovskite-type far-red phosphors.