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The electronic and optical properties of a narrow-band red-emitting nanophosphor K2NaGaF6:Mn4+ for warm white light-emitting diodes†
Journal of Materials Chemistry C ( IF 5.7 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1039/c7tc05098d Chunyan Jiang 1, 2, 3 , Mikhail G. Brik 3, 4, 5, 6, 7 , Lihua Li 1, 2, 3 , Liyi Li 1, 2, 3 , Jie Peng 1, 2, 3 , Jianan Wu 1, 2, 3 , Maxim S. Molokeev 8, 9, 10, 11, 12 , Ka-Leung Wong 3, 13, 14 , Mingying Peng 1, 2, 3, 15, 16
Journal of Materials Chemistry C ( IF 5.7 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1039/c7tc05098d Chunyan Jiang 1, 2, 3 , Mikhail G. Brik 3, 4, 5, 6, 7 , Lihua Li 1, 2, 3 , Liyi Li 1, 2, 3 , Jie Peng 1, 2, 3 , Jianan Wu 1, 2, 3 , Maxim S. Molokeev 8, 9, 10, 11, 12 , Ka-Leung Wong 3, 13, 14 , Mingying Peng 1, 2, 3, 15, 16
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Recently, as a key red component in the development of warm white light-emitting diodes (WLEDs), Mn4+-doped fluorides with narrow red emission have sparked rapidly growing interest because they improve color rendition and enhance the visual energy efficiency. Herein, a red nanophosphor, K2NaGaF6:Mn4+, with a diameter of 150–250 nm has been synthesized using a simple co-precipitation method. Rietveld refinement reveals that it crystallizes in the space group Fm![[3 with combining macron]](https://www.rsc.org/images/entities/char_0033_0304.gif)
m with the cell parameter a = 8.25320(4) Å. The exchange charge model (ECM) has been used to calculate the energy levels of Mn4+ ions in K2NaGaF6, which match well with the experimental spectra. The as-synthesized phosphor exhibits a narrow red emission at around 630 nm (spin-forbidden 2Eg → 4A2 transition of Mn4+ ions) when excited at 365 nm (4A2g → 4T1g) and 467 nm (4A2g → 4T2g), with a quantum efficiency (QE) of 61% and good resistance to thermal quenching. Based on the structure, the formation mechanism of ZPL has been discussed. In addition, the concentration-dependent decay curves of Mn4+ in K2NaGaF6 were fitted using the Inokuti–Hirayama model, suggesting that the dipole–dipole interactions determine the concentration quenching. Finally, encouraged by the good performance, a warm LED with a CRI of 89.4 and CCT of 3779 K was fabricated by employing the title nanophosphor as the red component. Our findings suggest that K2NaGaF6:Mn4+ can be a viable candidate for the red phosphor used in warm WLEDs.
中文翻译：
窄带红色发射纳米磷光体K 2 NaGaF 6：Mn 4+的电子和光学性质，用于暖白色发光二极管†
近年来，作为暖白光发光二极管（WLED）开发中的关键红色成分，具有窄红色发射的Mn 4+掺杂的氟化物引起了人们的迅速关注，因为它们改善了色彩再现性并提高了视觉能量效率。在此，使用简单的共沉淀法合成了直径为150–250 nm的红色纳米磷光体K 2 NaGaF 6：Mn 4+。Rietveld精炼显示，它在单元参数a = 8.25320（4）Å的空间群Fmm中结晶。交换电荷模型（ECM）已用于计算K 2 NaGaF 6中Mn 4+离子的能级，与实验光谱非常吻合。合成后的荧光粉在365 nm（4 A 2g → 4 T 1g）和467 nm（4A 2g → 4 T 1g）激发时，在630 nm附近呈现窄的红色发射（Mn 4+离子的自旋禁止2 E g → 4 A 2跃迁）。4 A 2g → 4 T 2g），量子效率（QE）为61％，并且具有良好的抗热淬火性。在此基础上，对ZPL的形成机理进行了探讨。此外，Mn 2+在K 2中的浓度依赖性衰减曲线NaGaF 6使用Inokuti-Hirayama模型拟合，表明偶极-偶极相互作用决定了浓度猝灭。最后，在良好的性能的鼓励下，采用标题纳米磷光体作为红色组分，制成了CRI为89.4和CCT为3779 K的暖色LED。我们的发现表明，K 2 NaGaF 6：Mn 4+可能是用于暖色WLED中的红色荧光粉的可行候选物。
更新日期：2018-02-22
m with the cell parameter a = 8.25320(4) Å. The exchange charge model (ECM) has been used to calculate the energy levels of Mn4+ ions in K2NaGaF6, which match well with the experimental spectra. The as-synthesized phosphor exhibits a narrow red emission at around 630 nm (spin-forbidden 2Eg → 4A2 transition of Mn4+ ions) when excited at 365 nm (4A2g → 4T1g) and 467 nm (4A2g → 4T2g), with a quantum efficiency (QE) of 61% and good resistance to thermal quenching. Based on the structure, the formation mechanism of ZPL has been discussed. In addition, the concentration-dependent decay curves of Mn4+ in K2NaGaF6 were fitted using the Inokuti–Hirayama model, suggesting that the dipole–dipole interactions determine the concentration quenching. Finally, encouraged by the good performance, a warm LED with a CRI of 89.4 and CCT of 3779 K was fabricated by employing the title nanophosphor as the red component. Our findings suggest that K2NaGaF6:Mn4+ can be a viable candidate for the red phosphor used in warm WLEDs.
中文翻译：
窄带红色发射纳米磷光体K 2 NaGaF 6：Mn 4+的电子和光学性质，用于暖白色发光二极管†
近年来，作为暖白光发光二极管（WLED）开发中的关键红色成分，具有窄红色发射的Mn 4+掺杂的氟化物引起了人们的迅速关注，因为它们改善了色彩再现性并提高了视觉能量效率。在此，使用简单的共沉淀法合成了直径为150–250 nm的红色纳米磷光体K 2 NaGaF 6：Mn 4+。Rietveld精炼显示，它在单元参数a = 8.25320（4）Å的空间群Fm
m中结晶。交换电荷模型（ECM）已用于计算K 2 NaGaF 6中Mn 4+离子的能级，与实验光谱非常吻合。合成后的荧光粉在365 nm（4 A 2g → 4 T 1g）和467 nm（4A 2g → 4 T 1g）激发时，在630 nm附近呈现窄的红色发射（Mn 4+离子的自旋禁止2 E g → 4 A 2跃迁）。4 A 2g → 4 T 2g），量子效率（QE）为61％，并且具有良好的抗热淬火性。在此基础上，对ZPL的形成机理进行了探讨。此外，Mn 2+在K 2中的浓度依赖性衰减曲线NaGaF 6使用Inokuti-Hirayama模型拟合，表明偶极-偶极相互作用决定了浓度猝灭。最后，在良好的性能的鼓励下，采用标题纳米磷光体作为红色组分，制成了CRI为89.4和CCT为3779 K的暖色LED。我们的发现表明，K 2 NaGaF 6：Mn 4+可能是用于暖色WLED中的红色荧光粉的可行候选物。
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