Mixed Microscopic Eu2+ Occupancies in the Next‐Generation Red LED Phosphor Sr[Li2Al2O2N2]:Eu2+ (SALON:Eu2+)

Red‐emitting narrow‐band phosphors are of utmost importance for next‐generation white‐light phosphor‐converted light‐emitting diodes (pc‐wLEDs) for improved efficacy and optimized correlated color temperatures. A promising representative crystallizing in an ordered variant of the UCr4C4 structure type is Sr[Li2Al2O2N2]:Eu2+ (SALON:Eu2+) emitting at a desirable wavelength of 614 nm. Despite an expected eightfold coordination of the Eu2+ ions by four N3− and O2− ions, respectively, the exact local coordination symmetry and a 1:1 ratio between the two types of ligands is not straightforwardly proven by X‐ray diffraction. Low‐temperature luminescence spectroscopy in conjunction with ligand field theory are powerful alternatives to resolve local features of Eu2+ as its excited 4f65d1 configuration reacts sensitively to the polarity of the ligands. The dominant emission at 614 nm shows pronounced vibronic fine structure at 10 K. In addition, weak emission bands can be resolved at 570 and 650 nm even at a low doping concentration of 0.5 mol% and are assigned to Eu2+ ions being eightfold coordinated by N3− and O2− ions in a ratio different from 1:1. Due to the feature of vierer ring‐type channels in SALON:Eu2+, those Eu2+ centers are sufficiently close for mutual energy transfer, which is characterized by time‐resolved luminescence at 10 K. The combination of high‐resolution photoluminescence spectroscopy at 10 K and X‐ray diffraction analysis on powdered samples of the red‐emitting phosphor Sr[Li2Al2O2N2]:Eu2+ (SALON:Eu2+) offers insights into structure–property relationships. With advanced ligand field calculations and time‐resolved studies, the complex emission spectrum can be explained by random local variations of the O:N ratio in the cube‐like coordination sphere of the embedded Eu2+ ions.