Crystallization of IR frequency‐doubling nanocrystals in chalcogenide glasses is a promising approach to achieve novel nonlinear optical materials. However, controllable glass crystallization remains challenging. In this study, IR‐transparent chalcogenide glass‐ceramics containing novel Cd₄GeS₆ IR frequency‐doubling nanocrystals (about 60‐80 nm) are fabricated through controlled nano‐crystallization. Nanocrystalline structure of the Cd₄GeS₆ nano‐crystallized glass‐ceramics is investigated in detail through X‐ray diffractometer, field emission scanning electron microscope, and Raman scattering techniques. The structural similarity of [Cd₄GeS₆] polyhedron in the network structure of as‐prepared glass is found to be responsible for the nucleation of Cd₄GeS₆ crystal. A unique microstructure of Cd₄GeS₆ nanocrystals embedded GeS₂ phase‐separated structure is discovered in samples thermally treated at high temperatures (370°C and 380°C). This study would not only shed more light on glass crystallization mechanism but also provide a feasible approach for the design and fabrication of new IR frequency‐doubling materials through glass crystallization.

中文翻译：

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硫属化物玻璃中红外倍频Cd4GeS6晶体的受控纳米晶化

硫族化物玻璃中红外倍频纳米晶体的结晶是一种获得新型非线性光学材料的有前途的方法。然而，可控的玻璃结晶仍然具有挑战性。在这项研究中，通过控制纳米结晶制备了包含新型Cd ₄ GeS ₆红外倍频纳米晶体（约60-80 nm）的红外透明硫族化物玻璃陶瓷。通过X射线衍射仪，场发射扫描电子显微镜和拉曼散射技术详细研究了Cd ₄ GeS ₆纳米晶化玻璃陶瓷的纳米晶体结构。[Cd ₄ GeS ₆发现在所制备玻璃的网络结构中的多面体是导致Cd ₄ GeS ₆晶体成核的原因。在高温（370°C和380°C）下热处理的样品中发现了Cd ₄ GeS ₆纳米晶体嵌入的GeS ₂相分离结构的独特微观结构。这项研究不仅将为玻璃结晶机理提供更多的信息，而且还将为通过玻璃结晶设计和制造新型IR倍频材料提供可行的方法。