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Title: Red-emitting manganese-doped aluminum nitride phosphor

Journal Article · · Optical Materials

Here, we report high efficiency luminescence with a manganese-doped aluminum nitride red-emitting phosphor under 254 nm 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, 10 atm N2 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 254 nm excitation (Q.E. = 0.86 ± 0.14) is obtained in aluminum nitride with a low manganese doping level of 0.06 mol.%. The principal Mn2+ decay of 1.25 ms 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.

Research Organization:
Ames Lab., Ames, IA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-07CH11358; AC02-76SF00515; AC52-07NA27344
OSTI ID:
1254325
Report Number(s):
IS-J--8996; LLNL-JRNL--681485; PII: S0925346716300696
Journal Information:
Optical Materials, Journal Name: Optical Materials Journal Issue: C Vol. 54; ISSN 0925-3467
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (40)

Fine Structure of Emission Spectra of the Red AIN:Mn Luminescence journal January 1966
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Some effects of oxygen impurities on AlN and GaN journal December 2002
High resolution soft X-ray absorption spectroscopy for the chemical state analysis of Mn journal September 2000
Analysis of vaporization kinetics of group-III nitrides journal January 1997
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides journal May 2013
Characterization of AlN:Mn thin film phosphors prepared by metalorganic chemical vapor deposition journal January 2007
Red emission from Mn2+ on a tetrahedral site in MgSiN2 journal June 2009
Synthesis and characterization of Mn-activated lithium aluminate red phosphors journal April 2013
A high efficiency rare earth-free orange emitting phosphor journal August 2015
Localised transitions in luminescence of AlN ceramics journal December 2014
Defects and luminescence control of AlN ceramic by Si-doping journal January 2016
Thermoluminescence of AlN. Influence of Synthesis Processes journal June 1995
Structural and luminescence studies of the new nitridomagnesoaluminate CaMg 2 AlN 3 journal January 2015
A novel and high brightness AlN:Mn2+ red phosphor for field emission displays journal January 2014
Optical Spectra of Exchange Coupled Mn ++ Ion Pairs in ZnS:MnS journal December 1963
Low-temperature metalorganic chemical vapor deposition of luminescent manganese-doped aluminum nitride films journal July 2005
Rationale for mixing exact exchange with density functional approximations journal December 1996
Origins of optical absorption and emission lines in AlN journal September 2014
Ab initiomolecular dynamics for liquid metals journal January 1993
Projector augmented-wave method journal December 1994
Periodic boundary conditions in ab initio calculations journal February 1995
Ab initio study of oxygen point defects in GaAs, GaN, and AlN journal December 1996
Theory of point defects in GaN, AlN, and BN: Relaxation and pressure effects journal September 1999
n -type doping of CuIn Se 2 and CuGa Se 2 journal July 2005
Intrinsic point defects in aluminum antimonide journal April 2008
Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion journal October 1991
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] journal February 1997
Luminescence Studies of Oxygen-Related Defects In Aluminum Nitride journal November 1990
Luminescence of Exchange Coupled Pairs of Transition Metal Ions journal January 2001
Phosphor Deterioration in Fluorescent Lamps journal February 1983
Luminescence in the System Al[sub 2]O[sub 3]-AIN journal January 1962
Luminescence Properties of Red Long-Lasting Phosphorescence Phosphor AlN:Mn 2+ journal January 2013
Photoluminescence Properties of Red-Emitting Mn 2+ -Activated CaAlSiN 3 Phosphor for White-LEDs journal January 2013
Concentration of point defects in wurtzite AlN: A hybrid functional study journal May 2012
Tunable luminescence Y_3Al_5O_12:006Ce^3+, xMn^2+ phosphors with different charge compensators for warm white light emitting diodes journal January 2012
Aerosol synthesis of AlN by nitridation of aluminum vapor and clusters journal March 1995
Formation of aluminum nitride from metal–organic precursors synthesized by reacting aluminum tri-chloride with bis(trimethylsilyl)carbodiimide journal January 2015
Rare-Earth Activated Nitride Phosphors: Synthesis, Luminescence and Applications journal June 2010
Influence of Si on the particle growth of AlN ceramics journal October 2014

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