Equivalent cation-tuning to realize a new Ce() fluoride with excellent comprehensive nonlinear optical performances

• Published in: Inorganic chemistry frontiers Vol. 11; no. 22; pp. 813 - 8138
• Main Authors: Zhang, Bei-Bei, Gao, Wen-Ye, Xu, Wei, Ma, Liang, Liu, Wenlong, Tang, Ru-Ling, Guo, Sheng-Ping
• Format: Journal Article
• Language: English
• Published: London Royal Society of Chemistry 05.11.2024
• Subjects: Cations; Cerium; Laser damage; Metal fluorides; Nonlinear optics; Optical properties; Potassium phosphates; Second harmonic generation; Silver gallium sulfide; Yield point
• ISSN: 2052-1553; 2052-1545; 2052-1553
• DOI: 10.1039/d4qi02088j

Exploring nonlinear optical (NLO) halide materials has become a hot research field owing to their diverse structures and excellent optical properties. In this paper, a new inorganic tetravalent cerium fluoride NH 4 Ce 3 F 13 was obtained. It crystallizes in the polar space group of Pmc 2 1 and exhibits a three-dimensional {[Ce 3 F 13 ] − } ∞ framework, which is composed of {[CeF 8 ] 4− } ∞ chains and {[CeF 6 ] 2− } ∞ layers formed by CeF 9 polyhedra, with the NH 4 + cation balancing the charge. NH 4 Ce 3 F 13 exhibits a strong second-harmonic generation (SHG) response among inorganic metal fluorides of about 1.2 times greater than that of KH 2 PO 4 (KDP) and a high laser-induced damage threshold (LIDT), which is 39 times more than that of AgGaS 2 . Besides, NH 4 Ce 3 F 13 possesses the largest band gap among Ce( iv )-containing NLO materials. This work provides a good case for exploring high-performance NLO fluoride materials. The acentric Ce( iv ) fluoride NH 4 Ce 3 F 13 is systematically studied, exhibiting the strong SHG effect (1.2 × KDP) and high LIDTs (39 × AGS). It also possesses the largest band gap among NLO materials containing Ce( iv ).