Jiang Ji-Hong, Zhang Lin-Chuan, Huang Ya-Xi, Sun Zhi-Mei, Pan Yuanming, Mi Jin-Xiao
Fujian Provincial Key Laboratory of Advanced Materials, Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, Fujian Province, People's Republic of China.
School of Materials Science and Engineering, Beihang University, Beijing 100191, People's Republic of China.
Dalton Trans. 2017 Jan 31;46(5):1677-1683. doi: 10.1039/c6dt04026h.
Two challenges to grow KBeBOF (KBBF), the best known deep-ultraviolet nonlinear optical (NLO) material to date, are the limited crystal sizes and the use of a highly toxic element (Be). Herein we report on the discovery of a novel anhydrous non-centrosymmetric alkali fluorinated borophosphate KB(PO)F (KBPF) featuring a cut-off wavelength of less than 200 nm and a large second-harmonic generation (SHG) effect similar to KHPO (KDP), hence representing a new promising deep-ultraviolet NLO material. The KBPF crystals consisting of common elements can be grown using green and cost effective processes and do not show any detectable hygroscopicity. The title compound also features a 2-dimensional layer [BPOF] built from [BOF] and [PO] tetrahedral groups but has much stronger interlayer bonds than KBBF, allowing the growth of large crystals. The title compound has been characterized by PXRD, SEM, TG-DSC, FTIR, UV-Vis-NIR diffuse reflectance and SHG analyses as well as single-crystal X-ray structure refinements. The optical properties of KBPF have also been evaluated by first-principles calculations at the density functional theory (DFT) level.
生长迄今为止最著名的深紫外非线性光学（NLO）材料KBeBOF（KBBF）面临两个挑战，即晶体尺寸有限以及使用剧毒元素（Be）。在此，我们报告发现了一种新型无水非中心对称碱金属氟硼酸磷酸盐KB(PO)F（KBPF），其截止波长小于200 nm，且具有与KHPO（KDP）相似的大二次谐波产生（SHG）效应，因此是一种有前景的新型深紫外NLO材料。由常见元素组成的KBPF晶体可以采用绿色且经济高效的工艺生长，并且不显示任何可检测到的吸湿性。标题化合物还具有由[BOF]和[PO]四面体基团构建的二维层[BPOF]，但其层间键比KBBF强得多，这使得能够生长出大晶体。标题化合物已通过粉末X射线衍射（PXRD）、扫描电子显微镜（SEM）、热重-差示扫描量热法（TG-DSC）、傅里叶变换红外光谱（FTIR）、紫外-可见-近红外漫反射和SHG分析以及单晶X射线结构精修进行了表征。KBPF的光学性质也已通过密度泛函理论（DFT）水平的第一性原理计算进行了评估。
