BaBi(SeO3)(2)Cl: a new polar material showing high second-harmonic generation efficiency enhanced by constructive alignment of chloride ions
BaBi(SeO3)(2)Cl: a new polar material showing high second-harmonic generation efficiency enhanced by constructive alignment of chloride ions
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BaBi(SeO3)(2)Cl：一种新型极性材料，通过氯离子的相长排列增强二次谐波产生效率
DOI：
10.1039/c5tc02925b
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发表时间：
2015
影响因子：
6.4
通讯作者：
Cheng Wen-Dan
中科院分区：
文献类型：
--
作者：
Geng Lei;Li Qiang;Meng Chang-Yu;Dai Kai;Lu Hong-Yan;Lin Chen-Sheng;Cheng Wen-Dan
首次采用水热法在200 °C的温和温度下合成了具有极性晶体结构的新型氯氧化物BaBi（SeO 3）2Cl。晶体属正交晶系Cmc 21（36）空间群，晶胞参数为a = 5.2804（2）Ω，B = 20.0535（9）Ω，c = 6.9070（3）Ω，V = 731.39（5）Ω 3，Z = 4。该化合物具有沿晶体学b轴方向沿着堆叠的二维[Bi（SeO 3）2Cl]2−阴离子层结构。在[Bi（SeO 3）2Cl]2−层中，BiO 4四棱锥通过共角的方式将Se（1）O3和Se（2）O3两种类型的三棱锥连接成[Bi（SeO 3）2]−链。[Bi（SeO 3）2]−链沿沿着c轴方向排列，氯离子与铋阳离子相邻，形成二维[Bi（SeO 3）2Cl]2−。因此，局部偶极矩的积木层的建设性的方式，这是有利的，以提高材料的二阶非线性性能的安排。利用粉末Kurtz-Perry方法评估了二次谐波产生（SHG）效率，表明具有较强的SHG效应（约为KH 2 PO 4（KDP）参考的16倍）。更令人兴奋的是，BaBi（SeO 3）2Cl可以实现I型相位匹配，这使得该化合物在实际应用中是可行的。此外，第一性原理密度泛函理论（DFT）计算也进行了说明晶体结构和光学性能之间的关系。
The novel oxychloride BaBi(SeO3)2Cl with polar crystal structure was first synthesized by using hydrothermal method at a mild temperature of 200 °C. It crystallizes in the orthorhombic Cmc21 (36) space group with cell parameters of a = 5.2804(2) Å, b = 20.0535(9) Å, c = 6.9070(3) Å, V = 731.39(5) Å3, and Z = 4. The compound features a two-dimensional [Bi(SeO3)2Cl]2− anionic layer structure stacking along the crystallographic b-axis direction. Within the [Bi(SeO3)2Cl]2− layer, BiO4 quadrangular pyramids bridge two types of Se(1)O3 and Se(2)O3 triangular pyramid through corner-sharing manner into a [Bi(SeO3)2]− chain. The [Bi(SeO3)2]− chains are aligned along c-axis direction with chloride ions adjacent to bismuth cations, and the 2D [Bi(SeO3)2Cl]2− forms. As a consequence, local dipole moments of the building block layers are arranged in a constructive fashion, which is favourable to enhance the second-order nonlinear properties of materials. Powder Kurtz–Perry method was utilized to evaluate the second-harmonic generation (SHG) efficiency, indicating a strong SHG effect (about 16 times that of KH2PO4 (KDP) reference). More excitingly, BaBi(SeO3)2Cl can achieve type I phase-matching, which make the compound feasible for practical applications. In addition, first-principles density functional theory (DFT) calculations were also performed to illustrate the relationships between crystal structure and optical properties.