基于钼坩埚密封法的ZnSe单晶生长及Cr2+掺杂特性研究

doi:10.15541/jim20250484

无机材料学报 ›› 2026, Vol. 41 ›› Issue (10): 1435-1441.DOI: 10.15541/jim20250484

基于钼坩埚密封法的ZnSe单晶生长及Cr²⁺掺杂特性研究

李亚¹^,²(), 黄昌保¹(), 余学舟¹, 祁华贝¹^,², 朱志成¹^,², 吴海信¹(), 陈伟豪¹^,², 余萍¹^,²

¹ 中国科学院合肥物质科学研究院, 安徽光学精密机械研究所, 安徽省光子器件与材料重点实验室, 合肥 230031
² 中国科学技术大学, 合肥 230026

收稿日期:2025-12-08 修回日期:2026-01-11 出版日期:2026-10-20 网络出版日期:2026-03-18
通讯作者: 黄昌保, 副研究员. E-mail: cbhuang@aiofm.ac.cn;
吴海信, 研究员. E-mail: hxwu@aiofm.ac.cn
作者简介:李亚(1996-), 男, 博士研究生. E-mail: liya11@mail.ustc.edu.cn

ZnSe Single Crystal Growth and Cr²⁺ Doping Behavior Enabled by a Molybdenum-crucible Sealing Method

LI Ya¹^,²(), HUANG Changbao¹(), YU Xuezhou¹, QI Huabei¹^,², ZHU Zhicheng¹^,², WU Haixin¹(), CHEN Weihao¹^,², YU Ping¹^,²

¹ Anhui Provincial Key Laboratory of Photonic Devices and Material, Anhui Institute of Optics and Fine Mechanics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China
² University of Science and Technology of China, Hefei 230026, China

Received:2025-12-08 Revised:2026-01-11 Published:2026-10-20 Online:2026-03-18
Contact: HUANG Changbao, associate professor. E-mail: cbhuang@aiofm.ac.cn;
WU Haixin, professor. E-mail: hxwu@aiofm.ac.cn
About author:LI Ya (1996-), male, PhD candidate. E-mail: liya11@mail.ustc.edu.cn

摘要/Abstract

摘要：

硒化锌(ZnSe)是一种具有低声子能量、宽透光范围和优良物化性能的II-VI族半导体材料, 在红外窗口和中红外激光基质等领域具有重要应用价值。然而, 在高温熔体生长过程中, ZnSe组分挥发不均衡, 导致化学计量比难以稳定控制, 从而制约了高品质单晶的制备。本研究围绕ZnSe单晶的稳定生长, 制定了一种基于密封熔体生长的制备技术路线。以气相法提纯的ZnSe多晶为原料, 通过钼坩埚真空密封抑制组分挥发, 并采用垂直布里奇曼法成功生长出尺寸为φ27 mm×100 mm的ZnSe单晶; 随后利用热扩散法制备Cr²⁺:ZnSe晶体元件。单晶摇摆曲线显示(110)面的半高宽为0.016° (57.6 arcsec), 表明晶体具有优异的结晶完整性; 透射光谱显示样品在1~15 μm波段呈现出接近理论透过率的高透过特性, 表明晶体具备良好的光学品质。电感耦合等离子体质谱测得Zn与Se原子比约为0.997, 说明密封生长可有效抑制化学计量比偏离。对于Cr²⁺:ZnSe样品, 吸收光谱在1770 nm处出现了Cr²⁺特征吸收峰(⁵E→⁵T₂), 且测试掺杂浓度约为1.81×10¹⁹ cm^-3; X射线光电子能谱进一步证实Cr主要以二价态存在。研究结果表明, 钼坩埚密封技术能够实现高质量ZnSe单晶生长, 且热扩散法可获得有效的Cr²⁺掺杂, 为高熔点、易挥发型中红外激光晶体的制备提供了可行的技术路径。

关键词: ZnSe单晶, 垂直布里奇曼法, 钼坩埚, Cr²⁺掺杂

Abstract:

Zinc selenide (ZnSe) is an II-VI semiconductor material with low phonon energy, a wide optical transparency range, and excellent physicochemical properties, making it highly attractive for infrared window components and mid-infrared laser host applications. However, during high-temperature melt growth, imbalanced volatilization of ZnSe components makes it difficult to maintain stoichiometric stability, thereby limiting the growth of high-quality single crystals. This study focused on the stable growth of ZnSe single crystals and established a preparation route based on sealed melt growth. Polycrystalline ZnSe purified by a vapor-phase method was used as the starting material. Component volatilization was suppressed by vacuum sealing in a molybdenum crucible, and ZnSe single crystals with dimensions of φ27 mm×100 mm were successfully grown using the vertical Bridgman method. Subsequently, Cr²⁺:ZnSe elements were prepared via thermal diffusion. X-ray rocking curve measurements revealed a full width at half maximum of 0.016° (57.6 arcsec) for the (110) plane, indicating high crystalline perfection. Optical transmittance spectra showed near-theoretical high transmittance in the wavelength range of 1-15 μm, demonstrating good optical quality of the crystals. Inductively coupled plasma-mass spectrometry analysis showed a Zn/Se atomic ratio of approximately 0.997, indicating that sealed growth effectively suppressed stoichiometric deviation. For the Cr²⁺:ZnSe samples, a characteristic Cr²⁺ absorption band centered at 1770 nm (⁵E→⁵T₂) was observed, and the Cr²⁺ doping concentration was measured to be 1.81×10¹⁹ cm^-3. X-ray photoelectron spectroscopy further confirmed that chromium predominantly existed in the divalent state. This study demonstrates that vacuum sealing using a molybdenum crucible enables the growth of high-quality ZnSe single crystals, and that thermal diffusion can achieve effective Cr²⁺ doping. These results provide a feasible technological pathway for preparing high-melting-point and volatile mid-infrared laser crystals.

Key words: ZnSe crystal, vertical Bridgman method, molybdenum crucible, Cr²⁺ doping

中图分类号:

李亚, 黄昌保, 余学舟, 祁华贝, 朱志成, 吴海信, 陈伟豪, 余萍. 基于钼坩埚密封法的ZnSe单晶生长及Cr²⁺掺杂特性研究[J]. 无机材料学报, 2026, 41(10): 1435-1441.

LI Ya, HUANG Changbao, YU Xuezhou, QI Huabei, ZHU Zhicheng, WU Haixin, CHEN Weihao, YU Ping. ZnSe Single Crystal Growth and Cr²⁺ Doping Behavior Enabled by a Molybdenum-crucible Sealing Method[J]. Journal of Inorganic Materials, 2026, 41(10): 1435-1441.

图/表 9

图1 晶体生长及温场示意图

Fig. 1 Schematic diagram of the crystal growth and temperature field

图2 热扩散实验装置示意图

Fig. 2 Diagram equipment of the thermal diffusion experiment

图3 PVT提纯结果

Fig. 3 Results of PVT purification (a) Photographs of purified ZnSe material; (b) XRD patterns of ZnSe before and after purification

表1 ZnSe中无机杂质的ICP-MS测试结果

Table 1 ICP-MS test results for inorganic impurities in ZnSe polycrystalline

Impurity	Commercial/(μg·g^-1)	Purification/(μg·g^-1)
Cu	0.030	0.01
Ag	0.017	0.01
Mg	0.070	0.06
Ni	0.020	0
Bi	0.050	0.01
In	0.040	0.03
Fe	0.300	0.10
Ca	0.400	0.20
Al	0.230	0.01
Na	0.110	0.10
Pb	0.050	0.02

图4 ZnSe晶体及其成分分析

Fig. 4 ZnSe crystal and its composition analysis (a) Photograph of the as-grown crystal ingot and crystal element; (b) EDS spectrum of the crystal sample

图5 ZnSe单晶(110)面的XRC

Fig. 5 XRC of (110) plane for ZnSe single crystal

图6 ZnSe晶体的透过光谱

Fig. 6 Transmittance spectra of ZnSe crystals (a) Vis-NIR transmittance spectra; (b) IR transmittance spectra

图7 ZnSe与Cr2+:ZnSe晶体的XPS谱图分析

Fig. 7 Comparative XPS analysis of ZnSe and Cr2+:ZnSe crystals (a) Zn2p and (b) Se3d high-resolution spectra of the ZnSe crystal; (c) XPS survey spectrum of the ZnSe crystal; (d) Zn2p, (e) Se3d and (f) Cr2p high-resolution spectra of the Cr2+:ZnSe crystal. Colorful figures are available on website

图8 Cr2+:ZnSe晶体在500~2500 nm波段的透过光谱和吸收系数

Fig. 8 Transmittance spectra and absorption coefficient of the Cr2+:ZnSe crystal in the wavelength range of 500-2500 nm (a) Transmittance spectrum; (b) Absorption coefficient

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基于钼坩埚密封法的ZnSe单晶生长及Cr²⁺掺杂特性研究

ZnSe Single Crystal Growth and Cr²⁺ Doping Behavior Enabled by a Molybdenum-crucible Sealing Method

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