Communication Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
Two-Dimensional Deep-Ultraviolet Beryllium-Free KBe2BO3F2 Family Nonlinear-Optical Monolayer Guoyu Yang†,‡ and Kechen Wu*,† †
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People’s Republic of China ‡ University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China S Supporting Information *
between the fluoride anion and potassium cation among the [Be2BO3F2]∞ (BBF) layers puts a limitation on the crystal thickness along the c axis. Moreover, toxic beryllium-bearing reagents add to the difficulty during crystal synthesis. In order to solve these problems, a great KBBF family was developed by substituting beryllium and potassium and reconstructing the BxOyFz network.18,19 In this work, we designed the 2D DUV−vis NLO monolayer Al3LiB2O6F4 (2D-ALBF) based on the BBF layer in KBBF. The general idea is that (a) planar BO3 and F, the main contributors to NLO, should be kept;17 (b) loose binding between layers suggests high-quality high-yield monolayer production;16 (c) in a 2D structure, substitution on beryllium also needs to retain the bond valence;20 (d) NLO enhancement from dimensionality compensates for the charge negativity in BBF network; (e) a blue shift by 2D moves the working range more into the DUV region to get over the “200 nm wall”. The calculation was performed with the Vienna ab initio simulation package.21 The absorption are calculated by Perdew− Burke−Ernzerhof (PBE),22 PBE0,23 and HSE06.24 Except for band calculations, the k points were all in a γ-centered Monkhorst−Pack scheme.25 NLO coefficients (dijk) were calculated by the length gauge method26−28 without scissor operator correction.29 Other details can be found in our previous work.30 As discussed before, 2D-ALBF is actually modified the BBF layer in KBBF. Specifically, in Figure 1a,b, the unit cell of 2DALBF corresponds to two unit cells of BBF and the four beryllium atoms are substituted by three aluminum atoms and
ABSTRACT: A two-dimensional (2D) nonlinear-optical (NLO) material could generate a breakthrough in the development of a nanoscale laser, especially in the range of high-energy and short-wavelength deep ultraviolet (DUV;
