An outstanding second-harmonic generation material BiB2O4F: exploiting the electron-withdrawing ability of fluorine. Issue 2 (12th January 2015)

• Record Type: Journal Article
• Authors: Cong, Rihong; Wang, Ying; Kang, Lei; Zhou, Zhengyang; Lin, Zheshuai; Yang, Tao
• Is Part Of: Inorganic chemistry frontiers. Volume 2:Issue 2(2015)
• Page Start: 170
• Page End: 176
• Publication Date: 2015-01-12
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c4qi00192c
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : The fluorine atoms in BiB2 O4 F withdraw the non-bonding electrons of Bi 3+ and thus strongly increase the SHG efficiency. Abstract : It is well known that the incorporation of fluorine usually blue-shifts the absorption edge of a crystal due to its large electronegativity. Herein, we validate the new functionality of fluorine that leads to the strong second harmonic generation (SHG) effect in a unique nonlinear optical (NLO) bismuth borate, BiB2 O4 F, where F coordinates to both B 3+ and Bi 3+ cations. The F-incorporation not only forms a more asymmetric unit [BO3 F] compared to the almost optical isotropic [BO4 ], but also withdraws the non-bonding electrons of Bi 3+, increasing its local polarization; thus the total SHG efficiency is increased significantly. Indeed, experimental measurements and first-principles calculations both support our anticipation that BiB2 O4 F is a phase-matchable NLO material with an exceptionally large SHG response. In order to further consolidate the functionality of fluorine, a comparison study with the structurally similar compound BiB2 O4 (OH) was performed.