We report high efficiency luminescence with a manganese-doped aluminum nitride redemitting 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 N 2 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 Mn 2+ 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 Mn 2+ 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.
Surface photovoltage spectroscopy (SPS) was used to observe photochemical charge separation and oxidation reactions on Fe 2 O 3 nanorod arrays under zero applied bias. Nanorod films were grown from FeCl 3 under hydrothermal conditions followed by calcination at 550 ºC. A negative photovoltage of up -130 mV is observed under 2.0 -4.5 eV (0.1 mW cm -2 ) illumination, confirming 2.0 eV as the effective bandgap of the material, and electrons as majority carriers. SPS in the presence of air, nitrogen, water, oxygen, and under vacuum suggest that the photovoltage is associated with the oxidation of surface water and with reversible surface hole trapping on the 1 min time scale and de-trapping on the 1 h time scale. O 2 promotes water oxidation by increasing the concentration of surface holes. Sacrificial donors KI, H 2 O 2 or potassium hydroxide increases the voltage to -240 and -400 mV, due to improved hole transfer. Cobalt oxide and Co-Pi cocatalysts quench the voltage, which is tentatively attributed to the removal of surface states and enhanced e/h recombination. An energy diagram is used to relate the experimental photovoltage to the built-in potentials at the respective interfaces.
We report on the development of two new mechanically rugged, high light yield transparent ceramic scintillators: (1) Ce-doped Gd-garnet for gamma spectroscopy, and (2) Eu-doped Gd-Lu-bixbyite for radiography. GYGAG(Ce) garnet transparent ceramics offer = 5.8g/cm 3 , Z eff = 48, principal decay of <100 ns, and light yield of 50,000 Ph/MeV. Gdgarnet ceramic scintillators offer the best energy resolution of any oxide scintillator, as good as R(662 keV) = 3% (Si-PD readout) for small sizes and typically R(662 keV) < 5% for cubic inch sizes. For radiography, the bixbyite transparent ceramic scintillator, (Gd,Lu,Eu) 2 O 3 , or "GLO," offers excellent x-ray stopping, with = 9.1 g/cm 3 and Z eff = 68. Several 10" diameter by 0.1" thickness GLO scintillators have been fabricated. GLO outperforms scintillator glass for high energy radiography, due to higher light yield (55,000 Ph/MeV) and better stopping, while providing spatial resolution of >8 lp/mm.
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 by 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. Figure 1
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