A near-UV excited, oxyfluoride phosphor solid solution Sr1.975Ce0.025Ba(AlO4F)1−x(SiO5)x has been developed for solid state white lighting applications. An examination of the host lattice, and the local structure around the Ce3+ activator ions through a combination of density functional theory, synchrotron X-ray and neutron powder diffraction and total scattering, and electron paramagnetic resonance, points to how chemical substitutions play a crucial role in tuning the optical properties of the phosphor. The maximum emission wavelength can be tuned from green (λem = 523 nm) to yellow (λem = 552 nm) by tuning the composition, x. Photoluminescent quantum yield is determined to be 70 ± 5% for some of the examples in the series. Excellent thermal properties were found for the x = 0.5 sample, with the photoluminescence intensity at 160 °C only decreased to 82% of its room temperature value. Phosphor-converted LED devices fabricated using an InGaN LED (λmax = 400 nm) exhibit high color rendering white light with Ra = 70 and a correlated color temperature near 7000 K. The value of Ra could be raised to 90 by the addition of a red component, and the correlated color temperature lowered to near 4000 K.
    
         
            
                 
             
                     
                    
                        
                            
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