Red-emitting manganese-doped aluminum nitride phosphor

• Published in: Optical materials 2016-04, Vol.54 (C), p.14-21
• Main Authors: Cherepy, Nerine J., Payne, Stephen A., Harvey, Nicholas M., Åberg, Daniel, Seeley, Zachary M., Holliday, Kiel S., Tran, Ich C., Zhou, Fei, Martinez, H. Paul, Demeyer, Jessica M., Drobshoff, Alexander D., Srivastava, Alok M., Camardello, Samuel J., Comanzo, Holly A., Schlagel, Deborah L., Lograsso, Thomas A.
• Format: Article
• Language: English
• Subjects: Aluminum nitride; Dopants; Doping; Lighting phosphor; Manganese; Manganese emission; MATERIALS SCIENCE; Nitride phosphor; Oxygen; Phosphors; Red phosphor; Spectra; Trapping
• ISSN: 0925-3467; 1873-1252
• DOI: 10.1016/j.optmat.2016.02.008

•AlN:Mn offers comparable absorbance and Q.E. under 254nm excitation to Y2O3:Eu.•AlN:Mn CIE coordinates (x=0.620, y=0.379); Y2O3:Eu (x=0.644, y=0.354).•AlN:Mn Q.E.=0.86±0.14, obtained with a low manganese doping level of 0.06mol.%.•DFT calculations show 254nm due to VAl coupled with oxygen impurities.•AlN:Mn exhibits excellent lumen maintenance in fluorescent lamp conditions. We report high efficiency luminescence with a manganese-doped aluminum nitride red-emitting phosphor under 254nm excitation, as well as its excellent lumen maintenance in fluorescent lamp conditions, making it a candidate replacement for the widely deployed europium-doped yttria red phosphor. Solid-state reaction of aluminum nitride powders with manganese metal at 1900°C, 10atmN2 in a reducing environment results in nitrogen deficiency, as revealed diffuse reflectance spectra. When these powders are subsequently annealed in flowing nitrogen at 1650°C, higher nitrogen content is recovered, resulting in white powders. Silicon was added to samples as an oxygen getter to improve emission efficiency. NEXAFS spectra and DFT calculations indicate that the Mn dopant is divalent. From DFT calculations, the UV absorption band is proposed to be due to an aluminum vacancy coupled with oxygen impurity dopants, and Mn2+ is assumed to be closely associated with this site. In contrast with some previous reports, we find that the highest quantum efficiency with 254nm excitation (Q.E.=0.86±0.14) is obtained in aluminum nitride with a low manganese doping level of 0.06mol.%. The principal Mn2+ decay of 1.25ms is assigned to non-interacting Mn sites, while additional components in the microsecond range appear with higher Mn doping, consistent with Mn clustering and resultant exchange coupling. Slower components are present in samples with low Mn doping, as well as strong afterglow, assigned to trapping on shallow traps followed by detrapping and subsequent trapping on Mn.