Influence of Additional Doping of Divalent Ions on Emission Intensity of Mn-Doped CaAl12O19
Authors: Sagayama Musashi , Zafari Umar , Subhoni Mekhrdod , Brik Mikhail , Yamamoto Tomoyuki 
Published: December 2020

In recent years, phosphor-converted white light-emitting diodes (pc-WLED) have great attention due to long lifetime and low power consumption compared to traditional lighting source. The most popular method to fabricate the pc-WLEDs is a combination of blue LED chips (GaN) and yellow phosphor (Y3Al5O12:Ce3+), which shows high luminescence intensity. However, such pc-WLED does not have high color rendering property due to the lack of red color emission component. In order to solve the problem and obtain warmer colored pc-WLEDs, it is efficient to incorporate a red phosphor in the pc-WLED. It is known that Mn-doped phosphor have been studied because of their broad excitation band in UV-blue region and their deep red emission. Among the oxide basis phosphors, several materials such as Mn-doped CaAl12O19 [1] and Mg2TiO4 [2] were reported with good luminescence property. To increase the emission efficiency, additional doping into such Mn-doped oxide phosphors were examined. The remarkable enhancement of the emission intensity was reported for Mg co-doping in Mn-doped CaAl12O19 [3]. However, the mechanism why such enhancement was achieved by co-doping has not yet been fully understood. In this study, influence of additional doping of divalent ions, such as Mg2+, Zn2+ and Cd2+, on the red-emission intensity of Mn-doped CaAl12O19 is investigated. All the samples were synthesized with conventional solid-state reaction method by changing divalent ions concentration. Crystal structure of the synthesized samples was characterized with the powder X-ray diffraction (XRD) technique. To determine the charge state and the local environment of Mn ions, the Electron Spin Resonance (ESR) spectra were observed.
The observed photoluminescence spectra of non-doped and Cd2+, Mg2+, Zn2+ co-doped CaAl12O19:Mn are shown in Fig. 1. In all cases, it is shown that divalent ions dopings could enhance the emission intensity, among which Mg2+ doping shows the largest enhancement. In the observed ESR spectra of non-doped and Cd2+, Mg2+, Zn2+ co-doped CaAl12O19:Mn, six peaks derived from hyper fine structure of Mn4+ could be seen in all the samples. It is noted that Mg and Zn co-doping significantly affects the spectral profiles, whereas only slight change was observed in Cd co-doped one. This indicates that Mg and Zn co-doping influence on local structure of Mn. In order to understand the effect of divalent ions doping on the enhancement of the red emission intensity, the first principles calculations within a density functional theory (DFT) have been also performed. As it is well known that the local environment of Mn ions is quite important on the emission intensity, local environment of Mn ions in CaAl12O19 were examined by substituting Mn ions at five crystallographically independent Al sites using the Vienna Ab initio Simulation Package (VASP)[4]. Using the same method, influence of additional dopings of divalent ions are investigated. In the conventional DFT calculations with local density approximation (LDA) or generalized gradient approximation (GGA) the band gap is always underestimated. As there are some methods developed recently to obtain more accurate band gap, for the electronic structure analysis, the modified Becke-Johnson potential by Tran and Blaha (TB-mBJ) [5] implemented in WIEN2k package [6] was employed here. In addition, Hubbard U correction on the d electron state is adopted to represent the strong correlation between d-electrons on Mn ions, which cannot be fully included in TB-mBJ.
Acknowledgement
This work was partially supported by the Joint Research Center for Environmentally Conscious Technologies in Materials Science (project No. 30009, 30012, 31008, and 31017) at ZAIKEN, Waseda University.
References
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Figure 1