Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, China.
J Am Chem Soc. 2015 Feb 18;137(6):2207-10. doi: 10.1021/ja5128314. Epub 2015 Feb 5.
A new beryllium-free borate Rb3Al3B3O10F has been synthesized and characterized by single-crystal X-ray diffraction. It features a framework structure consisting of alveolate [Al3(BO3)3OF]∞ layers tightly bound via Al-O and Al-F bridged bonds, with the in-layer BO3 groups in nearly coplanar and aligned arrangement. This compound is transparent down to 200 nm and is phase-matchable with a powder second-harmonic generation efficiency of 1.2 times that of KH2PO4. Remarkably, it exhibits a strong interlayer bonding which is about one order larger than that of the benchmark KBe2BO3F2, thus no layering tendency was observed during the crystal growth. In addition, it is nonhygroscopic and thermally stable up to ∼1462 K. These attributes make Rb3Al3B3O10F a promising nonlinear optical crystal in the deep-ultraviolet region. First-principles calculations, combined with the anionic group theory, were adopted to rationalize the optical properties.
一种新型无铍硼酸铷 Rb3Al3B3O10F 已被合成并通过单晶 X 射线衍射进行了表征。它具有由肺泡[Al3(BO3)3OF]∞层组成的骨架结构，通过 Al-O 和 Al-F 桥键紧密结合，层内BO3基团几乎共面且排列整齐。该化合物在 200nm 以下透明，与粉末二次谐波产生效率为 KH2PO4 的 1.2 倍的相匹配。值得注意的是，它表现出很强的层间键合，比基准 KBe2BO3F2 大约大一个数量级，因此在晶体生长过程中没有分层趋势。此外，它不吸湿，热稳定性高达约 1462K。这些特性使得 Rb3Al3B3O10F 成为深紫外非线性光学晶体中很有前途的候选材料。采用第一性原理计算，结合阴离子基团理论，对其光学性质进行了合理化解释。
