Polarization sensitive luminescence properties of europium ions in ZnO microrod matrix
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摘要:
针对基质晶格各向异性对稀土离子偏振发光特性的影响，采用水热法制备了ZnO微米棒及铕掺杂ZnO微米棒。对照研究发现，掺杂后的样品长径比增加，形貌由哑铃型转变为直微米棒。光学性质分析表明，385 nm处的束缚激子发光使得ZnO微米棒的紫外发光呈明显不对称线形，550 nm处观测到一个较弱的可见区发光。掺杂铕离子后，可见区域发光明显增强。对于Eu3+离子掺杂ZnO微米棒，532 nm激发下可观测到窄半峰宽的Eu3+离子特征发光峰。调节入射激发光的偏振方向时，Eu3+离子发光峰强度随偏振光角度呈周期性变化，且发光偏振度随掺杂浓度的增加而增大。结果表明，借助ZnO微米棒基质晶格可获得对激发光偏振敏感的铕离子发光。掺杂ZnO微米棒能够将低维ZnO材料的紫外光吸收性能与稀土离子优异的可见发光特性进行整合，使其在偏振光谱探测等领域具有重要的应用价值。
Abstract:Focusing on the influence of the matrix lattice anisotropy on the polarization luminescence of rare earth ions, ZnO microrods and europium-doped ZnO microrods were prepared using a hydrothermal method. Comparative studies have found that the length-to-diameter ratio of doped samples increases, and the morphology of the microrod changes from dumbbell-like to straight. Analysis of the optical properties shows that the bound exciton luminescence at 385-nm makes the UV luminescence of ZnO microrods appear asymmetrical, and a weak luminescence in visible region is observed at 550 nm. After europium ion doping, the luminescence in the visible region is enhanced. For Eu3+ doped ZnO microrods, Eu3+ ion characteristic luminescence peaks with narrow half width can be observed under 532-nm excitation. When the polarization direction of the incident excitation light is adjusted, the emission of Eu3+ ions changes periodically with the angle of the polarized light. The polarization degree increases as the doping concentration increases. These results show that the luminescence of the europium ions in the ZnO microrod matrix lattice is sensitive to the polarization of excited light. Doped ZnO microrods can integrate the ultraviolet absorption properties of low-dimensional ZnO materials with the excellent visible luminescence properties of rare earth ions, meaning they have significant application value in fields such as polarization detection.
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Key words:
- ZnO microrods /
- rare earth doped /
- polarization sensitive
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图 1 (a) ZnO和(b) ZnO:Eu (3%)微米棒的SEM图；(c) 掺杂前后ZnO微米棒的XRD谱及标准卡数据（插图是衍射峰的局部放大图）
Figure 1. SEM images of (a) ZnO and (b) ZnO:Eu(3%) microrods; (c) XRD spectra and standard card data of ZnO microrods before and after doping (Inset is a partial magnification of the diffraction peaks)
图 2 (a) 325 nm激发下掺杂前后单个ZnO微米棒PL光谱图（蓝色点划线是ZnO拟合后的分峰，红色点线是ZnO:Eu-3%拟合后的分峰）；(b) 532 nm激发下不同掺杂浓度的单个ZnO:Eu微米棒PL光谱图（插图是浓度猝灭曲线）
Figure 2. (a) PL spectra of a single ZnO microrod before and after doping under 325-nm excitation (the blue dot line is the peak fitting for ZnO, and the red dot line is the peak fitting for ZnO:Eu-3%); (b) PL spectra of a single ZnO:Eu microrod with different doping concentrations at 532-nm excitation (Inset is the concentration quenching curve)
图 3 ZnO和不同掺杂浓度ZnO:Eu微米棒紫外-可见吸收光谱图
Figure 3. Ultraviolet-visible absorption spectra of ZnO and ZnO:Eu microrods with different doping concentrations
图 4 ZnO和不同掺杂浓度ZnO:Eu微米棒的时间分辨PL光谱图。插图是根据ZnO和ZnO:Eu微米棒的时间分辨PL计算的衰减常数
Figure 4. Time-resolved PL spectra of ZnO and ZnO:Eu microrods with different doping concentrations. The illustration is the attenuation constant calculated from the time-resolved PL of ZnO and ZnO:Eu microrods
图 5 (a) 偏振敏感的发光特性测试光路图；(b)、(c)和(d) 532 nm激发下不同掺杂浓度ZnO:Eu微米棒发光峰值随偏振光角度变化图像
Figure 5. (a) Experimental setup for measuring the polarization-sensitive luminescence; (b), (c) and (d) The luminescence intensities of ZnO:Eu microrods with different doping concentrations vary with the angle of polarized light under of 532-nm excitation
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