Nontoxic KBBF Family Member Zn₂BO₃(OH): Balance between Beneficial Layered Structure and Layer Tendency

Abstract

The conflict between beneficial layered structure for performances and layered growth habits in KBe2BO3F2 (KBBF) always restricts its practical applications. A beryllium‐free KBBF family member, Zn2BO3(OH), is explored to feature the same topological layer with KBBF by replacing [BeO3F]5− with [ZnO3(OH)]5− and excellent UV performances. It exhibits a second harmonic generation response of about 1.5 × KH2PO4 with the UV cutoff edge of 204 nm. The birefringence of Zn2BO3(OH) in the visible region is about 0.067, which is larger than those of commercial UV crystals LiB3O5, CsB3O5, and CsLiB6O10. Additionally, it has excellent thermal and water‐resistant stabilities. Owing to the removal of interlayer cations, Zn2BO3(OH) shows better growth habits than KBBF while achieving the balance between beneficial layered structure and layer tendency.

π-Conjugated Trigonal Planar [C(NH2)3]+ Cationic Group: A Superior Functional Unit for Ultraviolet Nonlinear Optical Materials

“…Notably, this remarkable SHG efficiency is nearly triple that of KBBF (∼1.2 × KDP) and is comparable to those of some metal-containing KBBF family members, such as Rb 3 Al 3 B 3 O 10 F (1.2 × KDP), Cs 3 Zn 6 B 9 O 21 (3.3 × KDP), AZn 2 BO 3 X 2 (A = Na, K, Rb, and NH 4 ; X = Cl and Br) (2.5–3.01 × KDP), and Zn 2 BO 3 OH (∼1.5 × KDP). 15 , 27 − 29 It is well-known that in terms of KBBF-type compounds, their SHG contribution mainly stems from their coparallel planar (BO 3 ) 3– triangles units. Accordingly for GClO, the uniform alignment of planar [C(NH 2 ) 3 ] + triangle units should mainly be responsible for its SHG coefficients.…”

Rational Design of the Metal‐Free KBe2BO3F2⋅(KBBF) Family Member C(NH2)3SO3F with Ultraviolet Optical Nonlinearity

“…Thus, to design new beryllium‐free UV NLO crystals with the structural feature of KBBF, metal atoms, such as Zn and Al atoms, often four‐coordinate with O/X (X=F, Cl, Br) atoms are employed to substitute BeO 3 F tetrahedra of KBBF. Some successful examples are Rb 3 Al 3 B 3 O 10 F, Cs 3 Zn 6 B 9 O 21 , AZn 2 BO 3 X 2 (A=Na, K, Rb, NH 4 ; X=Cl, Br), and Zn 2 BO 3 OH . However, the growth of inorganic NLO crystal commonly require high cost and energy use.…”

Deep‐Ultraviolet Nonlinear‐Optical van‐der‐Waals Beryllium Borates**

“…Asimilar compound is Zn 2 BO 4 Hwith P2 1 symmetry,though it is opaque for the DUV light (l UV % 204 nm). [15] It is emphasized that 1T-BBH can exhibit excellent DUV NLO performance balance,w hich is almost identical to that of KBBF.This can also be well understood by aparallel study of the intrinsic NLO origin in BBH and KBBF,a ss hown in Figure 3. Figure 3a plots the partial density of states (PDOS), band-resolved SHG analysis and SHG density projection of…”