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 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

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, 2026, 41(10): 1435-1441.

Figures/Tables 9

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

Fig. 2 Diagram equipment of the thermal diffusion experiment

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

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

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

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

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

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

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

References 32

[1]	HUANG W, TANG G, WANG C, et al. Effect of different doping concentrations on the properties of Fe²⁺:ZnSe and Fe²⁺, Cr²⁺:ZnSe crystals grown by the chemical vapor transport method. Inorganic Chemistry, 2024, 63(47): 22605. DOI URL
[2]	LI Y, YANG D, NAN W, et al. The crystal growth of ZnSe by the traveling heater method with the accelerated crucible rotation technique. Journal of Crystal Growth, 2022, 589: 126684. DOI URL
[3]	DEGODA V Y, PODUST G P. Features of the dark conductivity of zinc selenide. Semiconductors, 2014, 48(3): 273. DOI URL
[4]	WEI Y, LIU C, MA E, et al. The optical spectra characterization of Cr²⁺:ZnSe polycrystalline synthesized by direct reaction of Zn-Cr alloy and element Se. Ceramics International, 2020, 46(13): 21136. DOI URL
[5]	WEI Y, LIU C, MA E, et al. Optical properties of mid-infrared Cr²⁺:ZnSe single crystals grown by chemical vapor transporting with NH₄Cl. Optical Materials Express, 2021, 11(3): 664. DOI URL
[6]	MIROV S B, MOSKALEV I S, VASILYEV S, et al. Frontiers of mid-IR lasers based on transition metal doped chalcogenides. IEEE Journal of Selected Topics in Quantum Electronics, 2018, 24(5): 1.
[7]	DELOACH L D, PAGE R H, WILKE G D, et al. Transition metal-doped zinc chalcogenides: spectroscopy and laser demonstration of a new class of gain media. IEEE Journal of Quantum Electronics, 1996, 32(6): 885. DOI URL
[8]	VASILYEV S, MOSKALEV I, MIROV M, et al. Recent breakthroughs in solid-state mid-IR laser technology. Laser Technik Journal, 2016, 13(4): 24.
[9]	PAGE R H, SCHAFFERS K I, DELOACH L D, et al. Cr²⁺-doped zinc chalcogenides as efficient, widely tunable mid-infrared lasers. IEEE Journal of Quantum Electronics, 1997, 33(4): 609. DOI URL
[10]	ADAMS J J, BIBEAU C, PAGE R H, et al. 4.0-4.5 µm lasing of Fe:ZnSe below 180 K, a new mid-infrared laser material. Optics Letters, 1999, 24(23): 1720. DOI URL
[11]	ALFORD W J, WAGNER G J, SULLIVAN A C, et al. High-power and Q-switched Cr:ZnSe lasers. Advanced Solid-State Photonics, San Antonio, 2003: 13.
[12]	SOROKIN E, SOROKINA I T, MIROV M S, et al. Ultrabroad continuous-wave tuning of ceramic Cr:ZnSe and Cr:ZnS lasers. Lasers, Sources and Related Photonic Devices, San Diego, 2010: AMC2.
[13]	MOSKALEV I, MIROV S, MIROV M, et al. 140 W Cr:ZnSe laser system. Optics Express, 2016, 24(18): 21090. DOI PMID
[14]	KORANDA P, JELíNKOVÁ H, ŠULC J, et al. ZnSe:Cr²⁺ coherently pumped laser. Optical Materials, 2007, 30(1): 149. DOI URL
[15]	FEDOROV V V, MIROV M S, MIROV S B, et al. Compact 1 J mid-IR Cr:ZnSe laser. Frontiers in Optics 2012/Laser Science XXVIII, Rochester, New York, 2012: FW6B.9.
[16]	VASILYEV S, MOSKALEV I, MIROV M, et al. Multi-Watt mid-IR femtosecond polycrystalline Cr²⁺:ZnS and Cr²⁺:ZnSe laser amplifiers with the spectrum spanning 2.0-2.6 μm. Optics Express, 2016, 24(2): 1616. DOI URL
[17]	NAGL N, GROBMEYER S, PERVAK V, et al. Directly diode- pumped, Kerr-lens mode-locked, few-cycle Cr:ZnSe oscillator. Optics Express, 2019, 27(17): 24445. DOI URL
[18]	WANG Y, FLEMING F, MCCRACKEN R A, et al. Hot-isostatic-pressed Cr:ZnSe ultrafast laser at 2.4 μm. Optics & Laser Technology, 2022, 154: 108300.
[19]	GIANNOTTI D, CARUSO A, PISANI F, et al. Comprehensive intensity and phase noise analysis of a femtosecond Cr:ZnSe Kerr-lens mode-locked laser. Optics & Laser Technology, 2025, 184: 112528.
[20]	KALINUSHKIN V P, GLADILIN A A, UVAROV O V, et al. Luminescence characteristics of chromium-doped by high- temperature diffusion CVD-ZnSe. Semiconductors, 2024, 58(4): 315. DOI
[21]	CHEN M, CUI H, LI W, et al. Reparative effect of diffusion process on host defects in Cr²⁺ doped ZnS/ZnSe. Journal of Alloys and Compounds, 2014, 597: 124. DOI URL
[22]	GAVRISHCHUK E M, GLADILIN A A, DANILOV V P, et al. Distribution of luminescence centers in the bulk of undoped, Fe-doped, and Cr-doped CVD ZnSe polycrystals studied by two-photon confocal microscopy. Inorganic Materials, 2016, 52(11): 1108. DOI
[23]	HU Q, HUANG C, WEI L, et al. Large-size high-quality CdSe-OPO component for far IR laser output prepared by directional crystal growth technique. CrystEngComm, 2023, 25(26): 3741. DOI URL
[24]	TRIBOULET R. The growth of bulk ZnSe crystals. Semiconductor Science and Technology, 1991, 6(9A): A18. DOI URL
[25]	RUDOLPH P, SCHÄFER N, FUKUDA T. Crystal growth of ZnSe from the melt. Materials Science and Engineering: R: Reports, 1995, 15(3): 85. DOI URL
[26]	WANG J F, OMINO A, ISSHIKI M. Melt growth of twin-free ZnSe single crystals. Journal of Crystal Growth, 2000, 214/215: 875. DOI URL
[27]	AVETISSOV I, CHANG K, ZHAVORONKOV N, et al. Nonstoichiometry and luminescent properties of ZnSe crystals grown from melt and vapor. Journal of Crystal Growth, 2014, 401: 686. DOI URL
[28]	LI H H. Refractive index of ZnS, ZnSe, and ZnTe and its wavelength and temperature derivatives. Journal of Physical and Chemical Reference Data, 1984, 13(1): 103. DOI URL
[29]	ZHANG H, FANG Y. Temperature dependent photoluminescence of surfactant assisted electrochemically synthesized ZnSe nanostructures. Journal of Alloys and Compounds, 2019, 781: 201. DOI URL
[30]	ZHANG T, ZHU G, ZHANG G, et al. CVT growth and optical properties of Cr,Fe:ZnSe single crystals for mid-infrared laser applications. Optics & Laser Technology, 2025, 188: 113003.
[31]	ERIKSSON M, SAINIO J, LAHTINEN J. Chromium deposition on ordered alumina films: an X-ray photoelectron spectroscopy study of the interaction with oxygen. The Journal of Chemical Physics, 2002, 116(9): 3870. DOI URL
[32]	SU C H, FETH S, VOLZ M P, et al. Vapor growth and characterization of Cr-doped ZnSe crystals. Journal of Crystal Growth, 1999, 207(1): 35. DOI URL

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

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