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
计量
- 文章访问数: 229
- HTML全文浏览量: 97
- PDF下载量: 89
- 被引次数: 0
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

HTML全文

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⁺

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

图 4 Tb³⁺与Dy³⁺间能级跃迁示意图

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 导出CSV

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

下载: 导出CSV

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

下载: 导出CSV

参考文献(41)

[1]	唐连波, 付大友, 陈琦, 等. 碳量子点增强气液相化学发光检测二氧化碳[J]. 应用化学,2022,39(8):1294-1302. doi: 10.1016/j.apsusc.2020.146825 TANG L B, FU D Y, CHEN Q, et al. Enhanced gas-liquid chemiluminescence by carbon dots for determination of carbon dioxide[J]. Chinese Journal of Applied Chemistry, 2022, 39(8): 1294-1302. doi: 10.1016/j.apsusc.2020.146825
[2]	CARDOSO J P S, CORREIA M R, VERMEERSCH R, et al. Europium-implanted AlN nanowires for red light-emitting diodes[J]. ACS Applied Nano Materials, 2022, 5(1): 972-984. doi: 10.1021/acsanm.1c03654
[3]	丁寒. 基于NaYF4: Yb, Er上转换发光纳米材料的掌印和足迹增强显现[J]. 分析化学,2023,51(11):1774-1782. doi: 10.1063/1.4978855 DING H. Enhanced Development of Palmprints and FootprintsBased on NaYF4: Yb, Er Upconversion Luminescent Nanomaterials[J]. Chinese Journal of Analytical Chemistry, 2023, 51(11): 1774-1782. doi: 10.1063/1.4978855
[4]	郑天程, 李月, 刘钰铃, 等. Cs₂ZnCl₄∶Ce³⁺, Mn²⁺的合成及其多模发光性能[J]. 应用化学,2023,40(12):1613-1622. ZHENG Tian-Cheng, LI Yue, LIU Yu-Ling, et al. Synthesis and Multi-Mode Luminescence Properties of Cs₂ZnCl₄∶Ce³⁺,Mn²⁺[J]. Chinese Journal of Applied Chemistry, 2023, 40(12): 1613-1622.
[5]	LI D B, JIANG K, SUN X J, et al. AlGaN photonics: recent advances in materials and ultraviolet devices[J]. Advances in Optics and Photonics, 2018, 10(1): 43-110. doi: 10.1364/AOP.10.000043
[6]	王俊荣,孙倩倩,朱国庆,等. 稀土掺杂正交发光纳米晶:从基础到前沿应用[J]. 应用化学,2023,40(11):1475‐1493. WANG Jun-Rong,SUN Qian-Qian,ZHU Guo-Qing, et al. Rare-Earth-Doped Orthogonal Luminescent Nanocrystals:From Fundamentals to Frontier Applications[J]. Chinese Journal of Applied Chemistry, 2023, 40(11): 1475‐1493.
[7]	王晓莹,涂昊宇,李琪,等. 基于石墨烯掺杂的CuMOF/Cu(OH)₂纳米棒阵列自支撑电极的制备及用于葡萄糖检测[J]. 分析化学,2023,51(9):1441-1451. WANG X Y, TU H Y, LI Q, et al. Efficient Electrochemical Sensor for Glucose DetectionBased on Self-Supporting Electrode of Graphene DopedCuMOF/Cu(OH)₂ Nanorod Arrays[J]. Chinese Journal of Applied Chemistry, 2023, 51(9): 1441-1451.
[8]	DING SH J, LI H Y, ZHANG Q L, et al. The investigations of Dy: YAG and Dy, Tb: YAG as potentially efficient GaN blue LD pumped solid state yellow laser crystals[J]. Journal of Luminescence, 2021, 237: 118174. doi: 10.1016/j.jlumin.2021.118174
[9]	胡萍, 刘晓萌, 田颖, 等. 直接泵浦中红外Dy: PbGa₂S₄激光器研究进展[J]. 发光学报,2022,43(12):1905-1914. doi: 10.37188/CJL.20220203 HU P, LIU X M, TIAN Y, et al. Research progress of directly pumped mid-infrared Dy: PbGa₂S₄ lasers[J]. Chinese Journal of Luminescence, 2022, 43(12): 1905-1914. (in Chinese). doi: 10.37188/CJL.20220203
[10]	龚宏波, 胡伟晔, 黄秋婷, 等. 基于表面增强拉曼光谱技术对负电性分子的高灵敏定性分析[J]. 分析化学,2023,51(7):1213-1221. GONG H B, HU W Y, HUANG Q T, et al. Highly Sensitive Qualitative Analysis of ElectronegativeMolecules Based on Surface-enhanced Raman Spectroscopy[J]. Chinese Journal of Applied Chemistry, 2023, 51(7): 1213-1221.
[11]	BENZ F, STRUNK H P, SCHAAB J, et al. Tuning the emission colour by manipulating terbium-terbium interactions: terbium doped aluminum nitride as an example system[J]. Journal of Applied Physics, 2013, 114(7): 073518. doi: 10.1063/1.4818815
[12]	GUERRA J A, MONTAÑEZ L, WINNACKER A, et al. Thermal activation and temperature dependent PL and CL of Tb doped amorphous AlN and SiN thin films[J]. Physica Status Solidi C, 2015, 12(8): 1183-1186. doi: 10.1002/pssc.201400226
[13]	WANG W, WANG X B, ZHANG P, et al. Near-white emission observed in Dy doped AlN[J]. RSC Advances, 2016, 6(60): 54801-54805. doi: 10.1039/C6RA03815H
[14]	马海, 王晓丹, 李祥, 等. Eu³⁺, Dy³⁺共注入AlN薄膜结构和发光特性研究[J]. 光子学报,2020,49(8):0831001. doi: 10.3788/gzxb20204908.0831001 MA H, WANG X D, LI X, et al. Structure and luminescence properties of Eu³⁺ and Dy³⁺ Co-implanted AlN films[J]. Acta Photonica Sinica, 2020, 49(8): 0831001. (in Chinese). doi: 10.3788/gzxb20204908.0831001
[15]	BOLOGNESI G, PARISI D, CALONICO D, et al. Yellow laser performance of Dy³⁺ in co-doped Dy, Tb: LiLuF₄[J]. Optics Letters, 2014, 39(23): 6628-6631. doi: 10.1364/OL.39.006628
[16]	SUN Y, YU F, LIAO M S, et al. Visible emission and energy transfer in Tb³⁺/Dy³⁺ co-doped phosphate glasses[J]. Journal of the American Ceramic Society, 2020, 103(12): 6847-6859. doi: 10.1111/jace.17391
[17]	贾珂, 曾佳汇, 韩甜甜, 等. Dy³⁺单掺、Tb³⁺单掺和Tb³⁺/Dy³⁺共掺碲锗钡酸盐玻璃的发光性能研究[J]. 激光与光电子学进展,2022,59(15):1516012. JIA K, ZENG J H, HAN T T, et al. Luminescent performance study on Dy³⁺-doped, Tb³⁺-doped and Tb³⁺/Dy³⁺ codoped TeO₂-GeO₂-BaO glasses[J]. Laser & Optoelectronics Progress, 2022, 59(15): 1516012. (in Chinese).
[18]	RONG X, WANG X Q, CHEN G, et al. Residual stress in AlN films grown on sapphire substrates by molecular beam epitaxy[J]. Superlattices and Microstructures, 2016, 93: 27-31. doi: 10.1016/j.spmi.2016.02.050
[19]	SUMATHI R R. Bulk AlN single crystal growth on foreign substrate and preparation of free-standing native seeds[J]. CrystEngComm, 2013, 15(12): 2232-2240. doi: 10.1039/C2CE26599K
[20]	KALLEL T, DAMMAK M, WANG J, et al. Raman characterization and stress analysis of AlN: Er³⁺ epilayers grown on sapphire and silicon substrates[J]. Materials Science and Engineering: B, 2014, 187: 46-52. doi: 10.1016/j.mseb.2014.04.003
[21]	RUTERANA P, CHAUVAT M P, LORENZ K. Mechanisms of damage formation during rare earth ion implantation in nitride semiconductors[J]. Japanese Journal of Applied Physics, 2013, 52(11S): 11NH02. doi: 10.7567/JJAP.52.11NH02
[22]	WEI W W, PENG Y, WANG J B, et al. Temperature dependence of stress and optical properties in AlN films grown by MOCVD[J]. Nanomaterials, 2021, 11(3): 698. doi: 10.3390/nano11030698
[23]	WANG D, WANG X D, MA H, et al. Structure and cathodoluminescence properties of Dy³⁺ and Eu³⁺ co-doped AlN films[J]. Optical Materials, 2022, 128: 112366. doi: 10.1016/j.optmat.2022.112366
[24]	SARON K M A, HASHIM M R, FARRUKH M A. NH₃-free growth of GaN nanostructure on n-Si (111) substrate using a conventional thermal evaporation technique[J]. Journal of Crystal Growth, 2012, 349(1): 19-23. doi: 10.1016/j.jcrysgro.2012.03.046
[25]	李嘉豪, 韩军, 邢艳辉, 等. 不同Mo层厚度的AlN/Mo/Sc_0.2Al_0.8N复合结构上MOCVD外延GaN[J]. 发光学报,2023,44(6):1077-1084. doi: 10.37188/CJL.20220406 LI J H, HAN J, XING Y H, et al. GaN grown on sputtered AlN/Mo/Sc_0.2Al_0.8N composite structure with different Mo thickness[J]. Chinese Journal of Luminescence, 2023, 44(6): 1077-1084. (in Chinese). doi: 10.37188/CJL.20220406
[26]	HSOUNA N, BOUZIDI C. White luminescence and energy transfer studies in Tb³⁺-Eu³⁺ co-doped phosphate glasses[J]. Solid State Sciences, 2022, 134: 107053. doi: 10.1016/j.solidstatesciences.2022.107053
[27]	WANG Q SH, LI J H, ZHANG W, et al. Synthesis, and photoluminescence and magnetic properties of Tb-doped AlN single-crystalline nanobelts[J]. Journal of Luminescence, 2021, 236: 118089. doi: 10.1016/j.jlumin.2021.118089
[28]	RODRIGUES J, FIALHO M, MAGALHAES S, et al. Luminescence properties of MOCVD grown Al_0.2Ga_0.8N layers implanted with Tb[J]. Journal of Luminescence, 2019, 210: 413-424. doi: 10.1016/j.jlumin.2019.02.060
[29]	白海斌, 陈昕, 沙雪竹, 等. NaGd(MoO₄)₂: Tb³⁺荧光粉的温度及浓度依赖发光与荧光动力学温度传感[J]. 发光学报,2023,44(10):1770-1778. doi: 10.37188/CJL.20230165 BAI H B, CHEN X, SHA X ZH, et al. Temperature- and concentration-dependent luminescence and fluorescence dynamic temperature sensing of NaGd(MoO₄)₂: Tb³⁺ phosphors[J]. Chinese Journal of Luminescence, 2023, 44(10): 1770-1778. (in Chinese). doi: 10.37188/CJL.20230165
[30]	CAO R P, CHEN C P, CHENG F R, et al. Synthesis and luminescence properties of Eu³⁺, Dy³⁺ co-doped Ca₃Bi(PO₄)₃ single-phase phosphor[J]. Journal of Luminescence, 2023, 257: 119731. doi: 10.1016/j.jlumin.2023.119731
[31]	方高阳, 王燕, 游振宇, 等. Sr₃Gd(BO₃)₃: Dy³⁺/RE³⁺(RE=Tb, Eu)晶体的生长、发光性质及能量传递[J]. 发光学报,2022,43(11):1721-1732. doi: 10.37188/CJL.20220094 FANG G Y, WANG Y, YOU ZH Y, et al. Crystal growth, spectral properties and energy transfer mechanisms of Sr₃Gd(BO₃)₃: Dy³⁺/RE³⁺(RE=Tb, Eu) crystals[J]. Chinese Journal of Luminescence, 2022, 43(11): 1721-1732. (in Chinese). doi: 10.37188/CJL.20220094
[32]	LUO X, WANG X D, MENG H CH, et al. Structure and cathodoluminescence properties in Tb³⁺ and Eu³⁺ doped AlN films[J]. Physica Status Solidi (A), 2024, 221(4): 2300625. doi: 10.1002/pssa.202300625
[33]	VIJAYAKUMAR M, VISWANATHAN K, MARIMUTHU K. Structural and optical studies on Dy³⁺: Tb³⁺ co-doped zinc leadfluoro-borophosphate glasses for white light applications[J]. Journal of Alloys and Compounds, 2018, 745: 306-318. doi: 10.1016/j.jallcom.2018.02.211
[34]	JIAO Y H, WU X L, REN Q, et al. Photoluminescence and energy transfer of a color tunable phosphors: Sr₃La (BO₃)₃: Ln³⁺ (Ln = Dy, Eu, Tb) for warm white light UV-excited WLEDs[J]. Optics & Laser Technology, 2019, 109: 470-479.
[35]	NASTASI M, MAYER J W. Ion Implantation and Synthesis of Materials [M]. Berlin, Heidelberg: Springer, 2006.
[36]	SU L M, LIU Y J, LI G H, et al. Multicolor emission leading by energy transfer between Dy³⁺ and Eu³⁺ in wolframite InNbTiO₆[J]. Journal of Luminescence, 2020, 227: 117578. doi: 10.1016/j.jlumin.2020.117578
[37]	李敏, 孙晓园, 范小暄, 等. Sr₆Lu₂Al₄O₁₅: Tb³⁺荧光粉的发光特性[J]. 发光学报,2023,44(11):1940-1949. doi: 10.37188/CJL.20230147 LI M, SUN X Y, FAN X X, et al. Photoluminescence properties of Sr₆Lu₂Al₄O₁₅: Tb³⁺ phosphor[J]. Chinese Journal of Luminescence, 2023, 44(11): 1940-1949. (in Chinese). doi: 10.37188/CJL.20230147
[38]	DEXTER D L. A theory of sensitized luminescence in solids[J]. The Journal of Chemical Physics, 1953, 21(5): 836-850. doi: 10.1063/1.1699044
[39]	MILLER M P, WRIGHT J C. Multiphonon and energy transfer relaxation in charge compensated crystals[J]. The Journal of Chemical Physics, 1979, 71(1): 324-338. doi: 10.1063/1.438074
[40]	VIDYADHARAN V, MOHAN P R, JOSEPH C, et al. Luminescent characteristics of UV excited Sr_0.5Ca_0.5TiO₃: Pr³⁺ reddish-orange phosphor[J]. Materials Chemistry and Physics, 2016, 170: 38-43. doi: 10.1016/j.matchemphys.2015.12.016
[41]	MCCAMY C S. Correlated color temperature as an explicit function of chromaticity coordinates[J]. Color Research & Application, 1992, 17(2): 142-144.