大尺寸Er,Yb:YAG单晶的生长及其性能

doi:10.15541/jim20220646

无机材料学报 ›› 2023, Vol. 38 ›› Issue (3): 329-334.DOI: 10.15541/jim20220646

大尺寸Er,Yb:YAG单晶的生长及其性能

王志强¹(), 吴济安¹, 陈昆峰¹(), 薛冬峰²()

1.山东大学晶体材料国家重点实验室, 新一代半导体材料研究院, 济南250100
2.中国科学院深圳先进技术研究院, 多尺度晶体材料研究中心, 深圳 518055

收稿日期:2022-11-01 修回日期:2022-11-30 出版日期:2023-01-17 网络出版日期:2023-01-17
通讯作者: 陈昆峰, 教授. E-mail: Kunfeng.Chen@sdu.edu.cn;
薛冬峰, 教授. E-mail: df.xue@siat.ac.cn
作者简介:王志强(1998-), 男, 硕士. E-mail: wangzhiqiang@mail.sdu.edu.cn

Large-size Er,Yb:YAG Single Crystal: Growth and Performance

WANG Zhiqiang¹(), WU Ji’an¹, CHEN Kunfeng¹(), XUE Dongfeng²()

1. Institute of Novel Semiconductors, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
2. Multiscale Crystal Materials Research Center, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China

Received:2022-11-01 Revised:2022-11-30 Published:2023-01-17 Online:2023-01-17
Contact: CHEN Kunfeng, professor. E-mail: Kunfeng.Chen@sdu.edu.cn;
XUE Dongfeng, professor. E-mail: df.xue@siat.ac.cn
About author:WANG Zhiqiang (1998-), male, Master. E-mail: wangzhiqiang@mail.sdu.edu.cn
Supported by:
National Natural Science Foundation of China(51832007);National Natural Science Foundation of China(52220105010);Natural Science Foundation of Shandong Province(ZR2020ZD35);Qilu Young Scholars Program of Shandong University

摘要/Abstract

摘要：

Er³⁺和Yb³⁺共掺杂的YAG晶体是一种非常重要的光学晶体, 目前, 该晶体已经广泛应用于高功率固体激光器, 但是采用提拉法生长大尺寸、低缺陷的掺杂YAG晶体仍然面临很多挑战。本工作采用快速提拉法成功获得了直径为80 mm、长度为230 mm的Er³⁺和Yb³⁺共掺杂的YAG单晶。采用不同测试方法评价其结构、掺杂浓度、光吸收、发光性能和刻蚀缺陷。晶片不同位置的拉曼峰峰位以及半峰宽没有明显变化, 说明晶片中心和边缘部分的晶体结构和应变是均匀的。刻蚀结果表明, 腐蚀坑均匀分布在整个腐蚀表面上, 没有观察到位错腐蚀坑特征, 这意味着晶体接近完美。Er³⁺和Yb³⁺在不同波长下的强发光峰以及辉光放电质谱结果证明Er,Yb:YAG单晶中成功掺杂了稀土离子。本工作采用提拉法成功生长了大尺寸、低缺陷的Er,Yb:YAG单晶, 证实了快速生长方法对YAG晶体中掺杂双稀土离子是有效的。

关键词: YAG单晶, 稀土掺杂, 快速提拉法, 发光性能

Abstract:

Currently, although Er³⁺ and Yb³⁺ co-doped YAG crystals are widely used in high power solid state lasers, there are still many challenges in growing large size, low defect doped YAG crystals using the Czochralski (Cz) method. In this paper, large-sized Er³⁺ and Yb³⁺ co-doped YAG bulk crystal with a diameter of 80 mm and a length of 230 mm was obtained by the fast Cz growth method. Their structure, doping concentration, optical absorption, luminescence performances, and etching defects were evaluated.According to the Raman detecting results, there is no significant variation in the peak positions and full width at half maxima (FWHM) of the Raman peaks at different locations on the wafer, indicating that the crystal structure and strain at central and edge section of thel wafer are uniformity. The etching results show that the corrosion pits are evenly distributed over the entire corrosion surfacewithout dislocation corrosion pit, which means that the crystals are highly near perfect. Strong luminescence peaks of Yb³⁺ and Er³⁺ at different wavelengths and glow discharge mass spectrometry results demonstrate the successful doping of rare earth ions in Er,Yb:YAG single crystals. This work successfully used the Cz method to grow large-sized, low-defect Er,Yb:YAG single crystals, confirming that the fast growth method is effective for doping double rare-earth ions in YAG crystals.

Key words: YAG single crystal, rare earth doping, fast Cz growth method, luminescence property

中图分类号:

O782

王志强, 吴济安, 陈昆峰, 薛冬峰. 大尺寸Er,Yb:YAG单晶的生长及其性能[J]. 无机材料学报, 2023, 38(3): 329-334.

WANG Zhiqiang, WU Ji’an, CHEN Kunfeng, XUE Dongfeng. Large-size Er,Yb:YAG Single Crystal: Growth and Performance[J]. Journal of Inorganic Materials, 2023, 38(3): 329-334.

图/表 7

Fig. 1 Characteristics of as-grown Er,Yb:YAG single crystal and wafer (a) With diameter of 80 mm and length of 230 mm; (b) Wafer with a thickness of 1.5 mm; (c) XRD patterns for wafer and ground powder; (d) EDS pattern of the wafer

Fig. 2 Micrographs of wafer surface with (111) face (a, b) Before etching; (c, d) Etched in H3PO4 at 180 ℃ for 60 min

Fig. 3 Raman spectrum of Er,Yb:YAG

Fig. 4 Raman spectra of different points at Er,Yb:YAG wafer (a) Five points on a straight line; (b) Peak positions and FWHM obtained by Lorentz fitting at the 783 cm-1 band with nisets showing Er,Yb:YAG wafer and schematic diagram of Raman test points

Fig. 5 Optical absorption spectra of Er,Yb:YAG crystal in the range of 200-1050 nm at room temperature

Table 1 Correspondence between the experimentally observed absorption lines and energy levels of Er3+ in Er,Yb:YAG single crystal[11,33⇓⇓ -36]

Wavelength/nm	Assignment (from ground ⁴I_15/2)
255	⁴D_7/2
356	²K_15/2
364	²G_9/2
381	⁴G_11/2
407	²H_9/2
442	⁴F_3/2
450	⁴F_5/2
488	⁴F_7/2
518, 524	²H_11/2
542	⁴S_3/2
647, 655	⁴F_9/2
788	⁴I_9/2
961, 966	⁴I_11/2

Fig. 6 Emission spectra of Er,Yb:YAG crystal at room temperature (a) Excited by 382 nm; (b) Excited by 260 nm; Fluorescent decay curves of (c) 554 nm; (d) 405 nm emission; Colorful figures are available on website

参考文献 38

[1]	MA X G, LI X Y, LI J Q, et al. Pressureless glass crystallization of transparent yttrium aluminum garnet-based nanoceramics. Nature Communications, 2018, 9(1): 1175. DOI PMID
[2]	SUN C T, XUE D. Study on the crystallization process of function inorganic crystal materials. Scientia Sinica Technologica, 2014, 44(11): 1123. DOI URL
[3]	SUN C T, XUE D. Chemical bonding in micro-pulling down process: high throughput single crystal growth. Science China Technological Sciences, 2018, 61(11): 1776. DOI
[4]	CHUBB D L, PAL A M T, PATTON M O, et al. Rare earth doped yttrium aluminum garnet (YAG) selective emitters. Materials & Design, 2001, 22(7): 591. DOI URL
[5]	UPASANI M, BUTEY B, MOHARIL S V. Photoluminescence study of rare earth doped yttrium aluminum garnet-YAG:RE (RE: Eu³⁺, Pr³⁺ and Tb³⁺). Optik, 2016, 127(4): 2004. DOI URL
[6]	GEORGIOU E, MUSSET O, BOQUILLON J P, et al. 50 mJ/30 ns FTIR Q-switched diode-pumped Er:Yb:glass 1.54 μm laser. Optics Communications, 2001, 198(1/2/3): 147. DOI URL
[7]	MIERCZYK Z, KWASNY M, KOPCZYNSKI K, et al. Er³⁺ and Yb³⁺ doped active media for ‘Eye-Safe’ laser systems. Journal of Alloys and Compounds 2020, 300(1): 398.
[8]	YANG G, HAN J, LI X, et al. Growth of 8 inch Yb:YAG single crystal by Czochralski method. Journal of Synthetic Crystals, 2019, 48: 1216.
[9]	BAO R J, YU L, YE L H, et al. Compact and sensitive Er³⁺/Yb³⁺ co-doped YAG single crystal optical fiber thermometry based on up-conversion luminescence. Sensors and Actuators A: Physical, 2018, 269: 182. DOI URL
[10]	GUO Y, HUANG L, ZHOU J, et al. Czochralski growth and investigation on the photoluminescence properties of YAG:Er single crystal. Journal of Synthetic Crystals, 2019, 48: 24.
[11]	NIZHANKOVSKYI S V, KOZLOVSKYI A A, KOVALENKO N O, et al. Optical and luminescence properties of Er,Yb:YAG crystals grown by horizontal directional crystallization method. Functional Materials, 2019, 26(1): 35. DOI URL
[12]	SUN C T, XUE D. Chemical bonding theory of single crystal growth and its application to ϕ3'' YAG bulk crystal. CrystEngComm, 2014, 16(11): 2129. DOI URL
[13]	SUN C T, XUE D. Crystal growth: an anisotropic mass transfer process at the interface. Physical Chemistry Chemical Physics, 2017, 19(19): 12407. DOI PMID
[14]	YANG P Z, DENG P Z, XU J, et al. Growth of high-quality single crystal of 30at% Yb:YAG and its laser performance. Journal of Crystal Growth, 2000, 216(1-4): 348. DOI URL
[15]	XU X D, ZHAO Z W, SONG P X, et al. Growth of high-quality single crystal of 50at% Yb:YAG and its spectral properties. Journal of Alloys and Compounds, 2004, 364(1/2): 311. DOI URL
[16]	XU X D, ZHAO Z W, WANG H H, et al. Spectroscopic and thermal properties of Cr,Yb:YAG crystal. Journal of Crystal Growth, 2004, 262(1-4): 317. DOI URL
[17]	ZHU M D, QI H J, PAN M Y, et al. Growth and luminescent properties of Yb:YAG and Ca co-doped Yb:YAG ultrafast scintillation crystals. Journal of Crystal Growth, 2018, 490: 51. DOI URL
[18]	BOGAERTS A, GIJBELS R. New developments and applications in GDMS. Fresenius Journal of Analytical Chemistry, 1999, 364(5): 367. DOI URL
[19]	DI SABATINO M. Detection limits for glow discharge mass spectrometry (GDMS) analyses of impurities in solar cell silicon. Measurement, 2014, 50: 135. DOI URL
[20]	YANG P Z, DENG P Z, YIN Z W, et al. The growth defects in Czochralski-grown Yb:YAG crystal. Journal of Crystal Growth, 2000, 218(1): 87. DOI URL
[21]	YIN H B, DENG P Z, GAN F X. Defects in YAG:Yb crystals. Journal of Applied Physics, 1998, 83(7): 3825. DOI URL
[22]	HURRELL J P, PORTO S P S, CHANG I F, et al. Optical phonons of yttrium aluminum garnet. Physical Review, 1968, 173(3): 851. DOI URL
[23]	PAPAGELIS K, KANELLIS G, VES S, et al. Lattice dynamical properties of the rare earth aluminum garnets (RE₃Al₅O₁₂). Physica Status Solidi B-Basic Solid State Physics, 2002, 233(1): 134. DOI URL
[24]	CHEN Y F, LIM P K, LIM S J, et al. Raman scattering investigation of Yb:YAG crystals grown by the Czochralski method. Journal of Raman Spectroscopy, 2003, 34(11): 882. DOI URL
[25]	PAPAGELIS K, KANELLIS G, ARVANITIDIS J, et al. Phonons in rare-earth aluminum garnets and their relation to lattice vibration of AlO₄. Physica Status Solidi B-Basic Research, 1999, 215(1): 193. DOI URL
[26]	QIU H W, YANG P Z, DONG J, et al. The influence of Yb concentration on laser crystal Yb:YAG. Materials Letters, 2002, 55(1/2): 1. DOI URL
[27]	WANG T, ZHANG J, ZHANG N, et al. The characteristics of high-quality Yb:YAG single crystal fibers grown by a LHPG method and the effects of their discoloration. RSC Advances, 2019, 9(39): 22567. DOI URL
[28]	WANG X D, XU X D, ZENG X H, et al. Effects of Yb concentration on the spectroscopic properties of Yb:Y₃Al₅O₁₂. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2006, 63(1): 49. DOI URL
[29]	WANG X D, XU X D, ZHAO Z W, et al. Comparison of fluorescence spectra of Yb:Y₃Al₅O₁₂ and Yb:YAlO₃ single crystals. Optical Materials, 2007, 29(12): 1662. DOI URL
[30]	GUERASSIMOVA N, GARNIER N, DUJARDIN C, et al. X-ray-excited charge transfer luminescence in YAG:Yb and YbAG. Journal of Luminescence, 2001, 94: 11.
[31]	ZORENKO Y, GORBENKO V, SAVCHYN V, et al. Luminescence properties and energy transfer processes in YAG:Yb,Er single crystalline films. Radiation Measurements, 2013, 56: 134. DOI URL
[32]	SARDAR D K, RUSSELL C C, GRUBER J B, et al. Absorption intensities and emission cross sections of principal intermanifold and inter-stark transitions of Er³⁺ (4f¹¹) in polycrystalline ceramic garnet Y₃Al₅O₁₂. Journal of Applied Physics, 2005, 97(12): 123501. DOI URL
[33]	BURDICK G W, GRUBER J B, NASH K L, et al. Analyses of 4f¹¹ energy levels and transition intensities between stark levels of Er³⁺ in Y₃Al₅O₁₂. Spectroscopy Letters, 2010, 43(5): 406. DOI URL
[34]	ZHOU J, ZHANG W X, WANG L, et al. Fabrication, microstructure and optical properties of polycrystalline Er³⁺:Y₃Al₅O₁₂ ceramics. Ceramics International, 2011, 37(1): 119. DOI URL
[35]	SEKITA M, HANEDA H, SHIRASAKI S, et al. Optical spectra of undoped and rare‐earth‐(=Pr, Nd, Eu, and Er) doped transparent ceramic Y₃Al₅O₁₂. Journal of Applied Physics, 1991, 69(6): 3709. DOI URL
[36]	NIZHANKOVSKYI S V, KOZLOVSKYI A A, KOVALENKO N O, et al. Spectral properties of Er-doped yttrium aluminum garnet crystals grown by modified horizontal directional crystallization method. Functional Materials, 2018, 25(4): 646. DOI URL
[37]	BI F, DONG X T, WANG J X, et al. Facile electrospinning preparation and up-conversion luminescence performance of Y₃Al₅O₁₂:Er³⁺,Yb³⁺ nanobelts. Journal of Inorganic and Organometallic Polymers and Materials, 2014, 24(2): 407. DOI URL
[38]	KATARIA V, MEHTA D S. Investigation of concurrent emissions in visible, UV and NIR region in Gd₂O₂S:Er,Yb nanophosphor by diverse excitation wavelengths as a function of firing temperature. Optical Materials, 2019, 95: 109204. DOI URL

大尺寸Er,Yb:YAG单晶的生长及其性能

Large-size Er,Yb:YAG Single Crystal: Growth and Performance

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 38

相关文章 15

编辑推荐

Metrics

本文评价

[1]	马玲玲, 常江. Nd掺杂硅酸钙及其复合电纺丝膜的制备及性能研究[J]. 无机材料学报, 2021, 36(9): 974-980.
[2]	戴云, 张中晗, 苏良碧, 李金, 龙勇, 丁雨憧, 武安华. 激光加热基座法生长高质量Yb³⁺掺杂Y₃A_l5O₁₂单晶光纤[J]. 无机材料学报, 2021, 36(7): 761-765.
[3]	杨金萍, 季文玲, 张浩, 刘盼, 崔燚, 魏恒勇. Eu ³⁺掺杂的多孔锆酸镧粉体制备及发光性能研究[J]. 无机材料学报, 2019, 34(7): 727-733.
[4]	曾祥雄, 杨进超, 左联, 杨奔奔, 秦峻, 彭志航. Li/Ce/La共掺杂对CaBi₂Nb₂O₉陶瓷晶体结构及电学性能的影响[J]. 无机材料学报, 2019, 34(4): 379-386.
[5]	张庆福, 李臣, 宋志国, 李永进, 邱建备, 杨正文. F/Cl比对卤磷酸钙固溶体Bi离子掺杂位点及价态的调控[J]. 无机材料学报, 2017, 32(6): 661-666.
[6]	吴霜, 刘波, 陈士伟, 张娟楠, 刘小林, 顾牡, 黄世明, 倪晨, 薛超凡. Lu₂SiO₅: Ce³⁺透明薄膜制备及其发光性能研究[J]. 无机材料学报, 2016, 31(9): 948-954.
[7]	毛启楠, 李鹤, 季振国, 席俊华, 张峻, 孔哲. Eu²⁺和Dy³⁺掺杂浓度对Sr₂MgSi₂O₇材料的荧光和长余辉性能的影响[J]. 无机材料学报, 2016, 31(8): 819-826.
[8]	吴霜, 刘波, 邱志澈, 陈士伟, 张娟楠, 刘小林, 顾牡, 黄世明, 倪晨. LuTaO₄:Ln³⁺(Ln=Eu,Tb)透明薄膜制备改进与其发光性能研究[J]. 无机材料学报, 2016, 31(4): 372-376.
[9]	张志雄, 欧阳绍业, 张约品, 夏海平. 白光LED用Ba₂LaF₇: Pr³⁺微晶玻璃的发光性能研究[J]. 无机材料学报, 2016, 31(10): 1046-1050.
[10]	王运锋, 宋金璠, 唐晓燕, 胡冬梅. NaGd(WO₄)₂:Yb³⁺/Tm³⁺反蛋白石光子晶体的制备与上转换发光调制研究[J]. 无机材料学报, 2016, 31(10): 1058-1062.
[11]	殷海荣, 刘晶, 乔荫颇, 李艳肖, 张攀, 周沁, 杨晨. 锶含量对稀土Eu掺杂锶钙羟基磷灰石发光性能及取代位置的影响[J]. 无机材料学报, 2016, 31(10): 1103-1109.
[12]	张书娴, 崔博, 王宏志, 李耀刚, 张青红. 柔性Eu³⁺掺杂SiO₂纳米纤维薄膜的制备及其发光性能[J]. 无机材料学报, 2015, 30(7): 719-724.
[13]	彭霞, 李淑星, 刘学建,黄毅华, 黄政仁, 李会利. Eu²⁺/Tb³⁺掺杂的Sr₂Si₅N₈基荧光粉的制备与发光性能[J]. 无机材料学报, 2015, 30(4): 397-400.
[14]	李金生, 孙旭东, 李晓东, 刘绍宏, 朱琦. 硬脂酸盐熔融法合成(Y,Lu)AG:Ce荧光粉及荧光性能研究[J]. 无机材料学报, 2015, 30(2): 177-182.
[15]	彭霞, 李淑星, 刘学建, 黄政仁, 李会利. Sr₂Si₅N₈:Eu²⁺荧光粉的制备及其发光性能研究[J]. 无机材料学报, 2014, 29(12): 1281-1286.