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

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),表明具有优异的结晶完整性;透射光谱显示样品在1~15 μm波段内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, 垂直布里奇曼法生长, 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 (XRC) measurements revealed a full width at half maximum (FWHM) 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 (ICP-MS) 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 (XPS) 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 growth, 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, DOI: 10.15541/jim20250484.

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, DOI: 10.15541/jim20250484.

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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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