光谱学与光谱分析, 2017, 37 (8): 2619, 网络出版: 2017-08-30  

氟氧化物玻璃陶瓷中铒激活中心的双光子三光子与四光子近红外量子剪裁发光

Two-Photon, Three-Photon, Four-Photon Near-Infrared Quantum Cutting Luminescence of Er3+ Activator in Oxyfluoride Vitroceramics
作者单位
1 北京师范大学应用光学北京重点实验室与物理系, 北京 100875
2 中国科学院上海光学精密机械研究所, 上海 201800
3 上海应用技术大学材料科学与技术系, 上海 200235
摘要
研究了掺铒的氟氧化物玻璃陶瓷的双光子、 三光子与四光子近红外量子剪裁发光。 我们测量了掺铒的氟氧化物玻璃陶瓷的X 射线衍射谱、 吸收谱、 从可见到近红外的发光光谱与激发光谱。 当Er3+浓度从0.5%增加到2.0%, 发现铒离子的4I15/2→2G7/2, 4I15/2→4G9/2, 4I15/2→4G11/2, 4I15/2→2H9/2, 4I15/2→(4F3/2, 4F5/2), 4I15/2→4F7/2, 4I15/2→2H11/2, 4I15/2→4S3/2, 4I15/2→4F9/2, 与4I15/2→4I9/2红外激发谱峰的强度增加了大约5.64, 4.26, 2.77, 7.31, 6.76, 4.75, 2.40, 11.14, 2.88, 和4.61倍, 同时, 铒离子的4I15/2→2G7/2, 4I15/2→4G9/2, 4I15/2→4G11/2, 4I15/2→2H9/2, 4I15/2→(4F3/2, 4F5/2), 与4I15/2→4F7/2的可见激发谱峰的强度减小了1.36, 1.93, 3.43, 1.01, 2.24和2.28倍。 也就是说我们发现红外发光与激发的强度都增强了2~11倍, 与此相伴的可见的发光与激发强度都减小了一到三倍。 而且, 1 543.0与550.0 nm发光的激发谱不仅在峰值波长而且也在波峰形状上非常相近。 上述实验结果证实了所看到的现象为多光子近红外量子剪裁发光现象。 为了更好的分析量子剪裁的过程与机理, 还测量了主要的可见与红外发光强度随激发强度的改变; 发现所有可见和红外发光强度都基本上是随激发强度成线性变化关系; 其中, 可见的发光强度随激发强度的改变呈略大于线形一次幂的变化关系, 它是由于小的激发态吸收造成的; 而1 543.0 nm红外发光强度随激发强度的变化呈略小于线形一次幂的变化关系, 它即是量子剪裁发光的特征现象。 还发现4I9/2能级的双光子量子剪裁主要由{4I9/2→4I13/2, 4I15/2→4I13/2} ETr31-ETa01交叉能量传递所导致; 4S3/2能级的三光子量子剪裁主要由{4S3/2→4I9/2, 4I15/2→4I13/2} ETr53-ETa01和{4I9/2→4I13/2, 4I15/2→4I13/2} ETr31-ETa01交叉能量传递所导致; 2H9/2能级的四光子量子剪裁主要由{2H9/2→4I13/2, 4I15/2→4S3/2} ETr91-ETa05, {4S3/2→4I9/2, 4I15/2→4I13/2} ETr53-ETa01和{4I9/2→4I13/2, 4I15/2→4I13/2} ETr31-ETa01交叉能量传递所导致。 上述研究结果对目前的全球热点新一代量子剪裁太阳能电池很有价值。
Abstract
Two-photon, three-photon, and four-photon near-infrared quantum cutting luminescence of Er3+∶oxyfluoride vitroceramics are studied. X-ray diffraction, absorption, visible to near infrared luminescence and excitation spectra of Er3+-doped oxyfluoride vitroceramics have been measured. We found that when the concentration of the Er3+ ion increased from 0.5% to 2.0%, the infrared excitation spectra intensities of the Er3+ ion enhanced by approximately 5.64, 4.26, 2.77, 7.31, 6.76, 4.75, 2.40, 11.14, 2.88, and 4.61 times for the 4I15/2→2G7/2, 4I15/2→4G9/2, 4I15/2→4G11/2, 4I15/2→2H9/2, 4I15/2→(4F3/2, 4F5/2), 4I15/2→4F7/2, 4I15/2→2H11/2, 4I15/2→4S3/2, 4I15/2→4F9/2, and 4I15/2→4I9/2 transitions. Meanwhile, it can also be found that the visible excitation spectra intensity of the Er3+ ion decreased by approximately 1.36, 1.93, 3.43, 1.01, 2.24, and 2.28 times for the 4I15/2→2G7/2, 4I15/2→4G9/2, 4I15/2→4G11/2, 4I15/2→2H9/2, 4I15/2→(4F3/2, 4F5/2), and 4I15/2→4F7/2 absorption transitions of the Er3+ ion, respectively. That is to say, the samples exhibited a 2 to 11 times enhancement in both infrared luminescence and excitation intensities, with a concomitant one to three times decreasing of both visible luminescence and excitation intensities. Moreover, the excitation spectra of 1 543.0 and 550.0 nm luminescence were very similar both in shape and peak wavelength, confirming that the multiphoton near-infrared quantum cutting luminescence phenomena were found. In order to analyze the process and mechanism of quantum cutting better, we measured the variation of main visible and infrared luminescence intensity based on the excitation intensity. It found that all visible and infrared luminescence intensity was linear depended on the excitation intensity basically. In which, the variation of the visible luminescence intensity depended on the excitation intensity was slightly larger than linear. It is resulted from the very small absorption of excited state. The variation of the infrared 1 543.0 nm luminescence intensity depended on the excitation intensity was slightly smaller than linear. It is the characteristic phenomena of quantum cutting luminescence. It found that two-photon quantum cutting luminescence of 4I9/2 state mainly resulted from the {4I9/2→4I13/2, 4I15/2→4I13/2} ETr31-ETa01 cross-energy transfer process. Three-photon quantum cutting luminescence of the 4S3/2 state mainly result from the {4S3/2→4I9/2, 4I15/2→4I13/2} ETr53-ETa01 and {4I9/2→4I13/2, 4I15/2→4I13/2} ETr31-ETa01 cross-energy transfer process. Four-photon quantum cutting of 2H9/2 mainly results from the {2H9/2→4I13/2, 4I15/2→4S3/2} ETr91-ETa05, {4S3/2→4I9/2, 4I15/2→4I13/2} ETr53-ETa01 and {4I9/2→4I13/2, 4I15/2→4I13/2} ETr31-ETa01 cross-energy transfer process. These measured results are useful for the next-generation of quantum cutting solar cells, a current hot point globally.

陈晓波, 李崧, 郭敬华, 周固, 樊婷婷, 于春雷, 郑东, 赵国营, 陶京富, 林伟, 陈鸾, 胡丽丽. 氟氧化物玻璃陶瓷中铒激活中心的双光子三光子与四光子近红外量子剪裁发光[J]. 光谱学与光谱分析, 2017, 37(8): 2619. CHEN Xiao-bo, LI Song, GUO Jing-hua, ZHOU Gu, FAN Ting-ting, YU Chun-lei, ZHENG Dong, ZHAO Guo-ying, TAO Jing-fu, LIN Wei, CHEN Luan, HU Li-li. Two-Photon, Three-Photon, Four-Photon Near-Infrared Quantum Cutting Luminescence of Er3+ Activator in Oxyfluoride Vitroceramics[J]. Spectroscopy and Spectral Analysis, 2017, 37(8): 2619.

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