Department of Chemistry, University of Houston , 112 Fleming Building, Houston, Texas 77204-5003, United States.
Department of Materials Science and Engineering, Northwestern University , 2220 Campus Drive, Evanston, Illinois 60208-3108, United States.
J Am Chem Soc. 2016 Apr 13;138(14):4984-9. doi: 10.1021/jacs.6b02203. Epub 2016 Apr 5.
A family of six nonlinear optical (NLO) materials, A3B3CD2O14 (A = Sr, Ba, or Pb; B = Mg or Zn; C = Te or W; and D = P or V), has been synthesized and characterized. In addition to the synthesis and crystal structures, comprehensive characterization of these compounds includes second harmonic generation (SHG) measurements, theoretical calculations, infrared and diffuse reflectance spectroscopies, and thermogravimetric measurements. We find that all of the reported materials are SHG-active at 1064 nm, with responses ranging from 2.8 to 13.5 × KDP, and exhibit absorption edges in the mid- to deep-ultraviolet regime. By systematically replacing the A, B, C, and D cations, we are able to tune these properties and investigate the role of different NLO-active structural units in producing the SHG responses. Specifically, our electronic structure calculations reveal that the presence of Pb(2+) on the A-site and Te(6+) on the C-site is critical for generating a large SHG response. The synthesis and structure-property relationships described in this family of materials will enable the design and discovery of new NLO materials.
一个六元非线性光学（NLO）材料家族，A3B3CD2O14（A = Sr、Ba 或 Pb；B = Mg 或 Zn；C = Te 或 W；D = P 或 V），已经被合成并进行了特性研究。除了合成和晶体结构，这些化合物的综合特性研究还包括二次谐波产生（SHG）测量、理论计算、红外和漫反射光谱以及热重测量。我们发现所有报道的材料在 1064nm 处均具有 SHG 活性，响应范围从 2.8 到 13.5×KDP，并且在中深紫外区域具有吸收边缘。通过系统地取代 A、B、C 和 D 阳离子，我们能够调整这些性质，并研究不同的 NLO 活性结构单元在产生 SHG 响应中的作用。具体来说，我们的电子结构计算表明，A 位上的 Pb(2+)和 C 位上的 Te(6+)的存在对于产生大的 SHG 响应是至关重要的。该材料家族的合成和结构-性质关系将能够促进新 NLO 材料的设计和发现。
