Titanosilicates with Strong Phase-Matched Second Harmonic Generation Responses

J. Am. Chem. Soc. 2016, 138, 9061-9064. DOI: 10.1021/jacs.6b05327
Tzu-Ling Chao, Wen-Jung Chang, Shu-Han Wen, Yu-Qing Lin, Bor-Chen Chang,* and Kwang-Hwa Lii*

The search for new and efficient nonlinear optical (NLO) materials has been an active research because of their technological importance in laser applications. Although a large number of frequency-doubling oxides, phosphates, borates, and fluoride-containing borates were found, no transition metal silicate with useful NLO properties has been reported. We have now synthesized and grown crystals of two new titanosilicates, Li2K4[(TiO)Si4O12] and Li2Rb4[(TiO)Si4O12], by using a flux and supercritical hydrothermal method. Their unique 3D framework structures contain highly compressed TiO5 square pyramids which are arranged one over the other to form infinite ···Ti–O···Ti–O straight chains with alternating short and long Ti-O distances. These two materials meet the requirements for efficient second harmonic generation including lack of center of inversion symmetry, large susceptibility, phase matching, transmitting at wavelengths of interest, resistant to laser damage, and thermally stable. These attributes make them very attractive for frequency doubling materials.

(a) Perspective view of the structure of Li2K4[(TiO)Si4O12] along the c axis. Key: Yellow square pyramid, TiO5; green tetrahedron, SiO4; solid circle, Li; open circle, K.
(b) Section of the structure viewed along the b axis showing the connectivity between TiO5 and silicate chains.