Dy<sup>3+</sup>，Tb<sup>3+</sup>共掺氮化铝薄膜结构与发光特性

罗璇; 孟河辰; 王晓丹; 陈子航; 曾雄辉; 高晓冬; 郑树楠; 毛红敏

doi:10.37188/CO.2023-0219

Dy³⁺，Tb³⁺共掺氮化铝薄膜结构与发光特性

doi: 10.37188/CO.2023-0219

cstr: 32171.14.CO.2023-0219

罗璇^1,,
孟河辰^1,,
王晓丹^1, ,,
陈子航^1,,
曾雄辉^2, ,,
高晓冬^2,,
郑树楠^2,,
毛红敏^1,

1.
苏州科技大学物理科学与技术学院, 江苏苏州 215009
2.
中国科学院苏州纳米技术与纳米仿生研究所, 江苏苏州 215123

基金项目: 国家自然科学基金资助项目（No.61974158，No.61306004）；江苏省自然科学基金（No. BK20191456，No. BK20221263）；江苏省“十四五”光学工程重点学科项目资助（No. 2021135）；江苏省研究生科研创新计划项目资助（No. KYCX22_3266）

详细信息

作者简介:
王晓丹（1980—），女，辽宁锦州人，教授，硕士生导师，2008 年于中国科学院上海光学精密机械研究所获得博士学位，现为苏州科技大学物理科学与技术学院教授，主要从事光功能材料的制备、性能表征及光电器件方面的研究。E-mail：xiaodanwang@mail.usts.edu.cn

曾雄辉（1976—），男，湖南湘潭人，研究员，博士生导师，2005 年于中国科学院上海光学精密机械研究所获得博士学位，现为中国科学院苏州纳米技术与纳米仿生研究所研究员，主要从事宽禁带半导体材料制备、物性和结构研究。E-mail：xhzeng2007@sinano.ac.cn

中图分类号: TN304.3
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出版历程
- 收稿日期: 2023-12-07
- 修回日期: 2023-12-26
- 网络出版日期: 2024-05-11

Structure and cathodoluminescence properties of Dy³⁺ and Tb³⁺ doped AlN films

1.
School of Physical Science and Technology, Suzhou University of Science and Technology, Suzhou 215009, China
2.
Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China

Funds: Supported by National Natural Science Foundation of China (No. 61974158, No.61306004); Natural Science Fund of Jiangsu Province (No. BK20191456, No. BK20221263); Jiangsu Key Disciplines of the Fourteenth Five-Year Plan (No. 2021135); Postgraduate Research ＆ Practice Innovation Program of Jiangsu Province (No. KYCX22_3266)

More Information

Corresponding author: xiaodanwang@mail.usts.edu.cn; xhzeng2007@sinano.ac.cn

摘要

摘要:
通过离子注入方法，首次将Dy³⁺和Tb³⁺共掺入氮化铝(AlN)薄膜，并研究了其晶体结构、阴极荧光和能量传递机制。拉曼光谱(Raman)和X射线衍射(XRD)结果显示，在Tb³⁺剂量一定的情况下，Dy³⁺的注入会导致晶格内部压应力增大，随着Dy³⁺的持续注入，一部分点缺陷发生复合，内部部分压应力会得到释放。阴极荧光光谱(CL)显示，高剂量Tb³⁺注入下，随着Dy³⁺剂量的增加，Tb³⁺的发射强度与Dy³⁺的发射强度呈现出不同的变化趋势。进一步分析表明可能存在Tb³⁺的⁵D₄→⁷F₆至Dy³⁺的⁶H_15/2→⁴F_9/2的共振能量传递。通过研究发现在不同Tb³⁺和Dy³⁺注入剂量下，样品的发光颜色在黄绿色与橙黄色之间转变，色温在4042~5119K范围变化。由上述研究结果可知，通过改变Tb³⁺与Dy³⁺共注入的剂量比可以有效调控材料的发光色坐标与色温。
- 镝离子 /
- 铽离子 /
- 氮化铝 /
- 发光特性 /
- 能量传递
Abstract:
For the first time, Tb³⁺ and Dy³⁺ co-doped AlN films were prepared using ion implantation, and their crystal structure, cathodoluminescence properties and energy transfer mechanism were investigated. Raman scattering and X-ray diffraction results indicate that ion implantation of Dy³⁺ has caused increased compressive stress within the internal lattice when the dosage of Tb³⁺ remains constant. Continuous implantation led to the recombination of some point defects, resulting in a partial release of internal compressive stress. Cathodoluminescence spectra demonstrated that with high-dose Tb³⁺ implantation, the emission intensities of Tb³⁺ and Dy³⁺ exhibited different trends with increasing Dy³⁺ dosage. We propose the existence of a resonance energy transfer from Tb³⁺ ions ⁵D₄→⁷F₆ to Dy³⁺ ions ⁶H_15/2→⁴F_9/2 in AlN films. Finally, we observe that under different implantation dose of Dy³⁺ ions to Tb³⁺ ions, the emission color of the sample shifts between yellow-green and orange-yellow, with color temperatures ranging from 4042 to 5119K. Adjusting the dose ratio of Dy³⁺ to Tb³⁺ enables effective control of chromaticity coordinates and color temperatures.
- dysprosium ions /
- terbium ions /
- aluminum nitride /
- luminescent properties /
- energy transfer

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图 1 (a) 样品S1~S3及(b) S4~S6的Raman光谱。插图给出了E₂(high)随着不同剂量Dy³⁺注入下的变化趋势

Figure 1. Raman spectra of (a) S1, S2, S3 samples and (b) S4, S5, S6 samples. The inset shows the trend of E₂(high) changes with different doses of Dy³⁺

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图 2 Tb³⁺和Dy³⁺注入AlN薄膜(a) S1~S3及(b) S4~S6 X射线衍射图，虚线标出了Bragg峰位置变化

Figure 2. X-ray diffractograms of Tb³⁺ and Dy³⁺ implanted AlN films. (a) S1-S3 samples; (b) S4-S6 samples. The dashed line indicates the change in Bragg peak position

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图 3 不同剂量下，Tb³⁺与Dy³⁺注入AlN的CL光谱图。(a) S1~S3样品；(b) S4~S6样品。(c), (d) Tb³⁺发光峰(I₄₉₃)和Dy³⁺发光峰(I₄₈₄)积分强度变化趋势

Figure 3. Cathodoluminescence (CL) spectra of AlN with different dosages of Tb³⁺ and Dy³⁺ injected. (a) S1-S3 samples; (b) S4-S6 samples. (c), (d) The variation trend of integrated intensities of Tb³⁺ emission peak (I₄₉₃) and Dy³⁺ emission peak (I₄₈₄)

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图 4 Tb³⁺与Dy³⁺间能级跃迁示意图

Figure 4. Energy transfer mechanism in the Tb³⁺ and Dy³⁺

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图 5 I₀/I与C_p^n/3 (n = 6、8和10)的线性拟合，当n = 6时观察到最佳拟合结果

Figure 5. Linear fitting between I₀/I and C_p^n/3 (n = 6, 8, 10), with the best fitting result observed when n = 6

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图 6 AlN: Tb³⁺,Dy³⁺样品发光色度坐标图

Figure 6. The CIE chromaticity diagram of the Tb³⁺ and Dy³⁺ co-doped AlN films

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表 1 AlN: Tb³⁺/Dy³⁺样品中离子注入剂量

Table 1. Ion implantation dose in AlN: Tb³⁺/Dy³⁺ samples

Sample	Tb³⁺(at/cm²)	Dy³⁺(at/cm²)
S1	5×10¹⁴	1×10¹⁴
S2	5×10¹⁴	5×10¹⁴
S3	5×10¹⁴	1×10¹⁵
S4	1×10¹⁵	1×10¹⁴
S5	1×10¹⁵	5×10¹⁴
S6	1×10¹⁵	1×10¹⁵

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表 2 平均注入剂量C_p，临界距离R_c计算结果

Table 2. Calculation results of average injection dose C_p and critical distance R_c

Sample	Tb³⁺ / （at· cm⁻²）	Dy³⁺/ （at· cm⁻²）	C_p/ （%, atom fraction）	R_c（nm）
S1	5×10¹⁴	1×10¹⁴	0.4219	2.11448
S2	5×10¹⁴	5×10¹⁴	0.7012	1.78531
S3	5×10¹⁴	1×10¹⁵	1.0480	1.56149
S4	1×10¹⁵	1×10¹⁴	0.7708	1.72986
S5	1×10¹⁵	5×10¹⁴	1.0480	1.56149
S6	1×10¹⁵	1×10¹⁵	1.3927	1.42028

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表 3 不同剂量的Tb³⁺和Dy³⁺注入样品时的色度坐标与色温

Table 3. Luminescent chromaticity coordinates and color temperature of AlN: Tb³⁺/Dy³⁺ with different doses of Tb³⁺and Dy³⁺ions

Sample	Tb³⁺/(at·cm⁻²)	Dy³⁺/(at·cm⁻²)	CIE co-ordinates		CCT/K
Sample	Tb³⁺/(at·cm⁻²)	Dy³⁺/(at·cm⁻²)	x	y	CCT/K
S1	5×10¹⁴	1×10¹⁴	0.3446	0.3939	5119.6625
S2	5×10¹⁴	5×10¹⁴	0.3775	0.3701	4042.5739
S3	5×10¹⁴	1×10¹⁵	0.3506	0.3566	4817.7583
S4	1×10¹⁵	1×10¹⁴	0.3560	0.4158	4845.6823
S5	1×10¹⁵	5×10¹⁴	0.3685	0.3714	4310.2723
S6	1×10¹⁵	1×10¹⁵	0.3422	0.3506	5110.9489

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