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

doi:10.15541/jim20250484

Abstract

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

CLC Number:

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

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