中远红外非线性光学晶体研究进展

3—5μm和8—12μm波段中远红外激光,在国防和民用领域均具有广泛的应用,作为全固态激光频率转换系统的核心部件,非线性光学晶体需要不断地优化和发展.本文从红外非线性光学晶体材料组成角度出发,总结了几种具有重大应用前景的磷族化合物(ZnGeP_2,CdSiP_2)、硫属化合物(CdSe, GaSe, LiInS_2系列,BaGa_4S_7系列)以及准位相匹配晶体(OP-GaAs, OP-GaP)等中远红外波段非线性光学晶体的研究进展.

Research progress of mid-and far-infrared nonlinear optical crystals

High-power tunable mid-infrared (MIR) and far-infrared (FIR) lasers in a range of 3-20 μm, especially in the atmospheric windows of 3-5 μm and 8-12 μm are essential for the applications, such as in remote sensing, minimally invasive surgery, telecommunication, national security, etc. At present, the technology of MIR and FIR laser have become a research hotspot. As the core component of all-solid-state laser frequency conversion system, nonlinear optical (NLO) crystals for coherent MIR and FIR laser are urgently needed by continuously optimizing and developing. However, compared with several outstanding near infrared, visible, and ultraviolet NLO crystals, such as β-BaB₂O₄, LiB₃O₅, LiNbO₃, KTiOPO₄, and KBe₂BO₃F₂, the generation of currently available NLO crystals for 3-20 μm laser is still underdeveloped. Traditional NLO oxide crystals are limited to output wavelengths ≤ 4 μm due to the multi-phonon absorption. In the past decades, the chalcopyrite-type AgGaS₂, AgGaSe₂ and ZnGeP₂ have become three main commercial crystals in the MIR region due to their high second-harmonic generation coefficients and wide IR transparency ranges. Up to now, ZnGeP₂ is still the state-of-the-art crystal for high energy and high average power output in a range of 3-8 μm. Unfortunately, there are still some intrinsic drawbacks that hinder their applications, such as in poor thermal conductivity and low laser damage threshold for AgGaS₂, non-phase-matching at 1.06 μm pumping for AgGaSe₂, and harmful two-photon absorption at 1.06 μm for ZnGeP₂. In addition, ZnGeP₂ has significant multi-phonon absorption in an 8-12 μm band, which restricts its applications in long wavelength MIR. With the development of research, several novel birefringent crystals, as well as all-epitaxial processing of orientation-patterned semiconductors GaAs (OP-GaAs) and GaP (OP-GaP), have been explored together with attractive properties, such as large NLO effect, wide transparency ranges, and high resistance to laser damage.In this paper, from the angle of the compositions of NLO crystal materials, several kinds of phosphide crystals (ZnGeP₂ CdSiP₂) and chalcogenide crystals (CdSe, GaSe, LiInS₂ series, and BaGa₄S₇ series) are summarized. In addition, the latest achievements of the orientation-patterned materials such as OP-GaAs and OP-GaP are also reviewed systematically. In summary, we review the above-mentioned attractive properties of these materials such as in the unique capabilities, the crystal growth, and the output power in the MIR and FIR region.