Second-order nonlinear optical crystals with mixed anions

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

“…Theasymmetric units of both 1 and 2 contain two Ba, one Ga, three I, four F, and nine Oa toms,a ll of which sit on general sites.T he Ga atom is sixfold-coordinated by two O atoms from two IO 3 À groups,a nd four terminal Fa toms (Figures 1a and b). TheG a À Ob ond lengths (1.988(4) and 2.019(4) in 1 and 2.020(8) and 2.013 (8) in 2)a re slightly longer than the GaÀFbond lengths (1.828(4) to 1.894(4) in 1 and 1.790 (8) (2) is coordinated by two Fa toms and ten Oa toms from eight IO 3 À groups.T he BaÀOb onds range from 2.749(4) to 3.216(4) and the Ba-F bonds range from 2.645(4) to 3.257(4) .In2,Ba(1) is tenfold-coordinated to five F À anions and five Oatoms from four IO 3 groups and Ba(2) is 12-fold coordinated by two F À anions and ten O atoms from eight IO 3 À groups.T he Ba À Ob onds range from 2.749(4) to 2.995 (9) and the Ba-F bonds range from 2.645(4) to 3.257(4) .These BaÀO, BaÀF, GaÀF, GaÀO, and IÀObonds are comparable to those reported previously. [27,43] Thev alues of the bond valence sum (BVS) have been calculated to verify the oxidation states of the Ba, Ga, and I atoms.T he calculated BVS values are 2.191, 1.881, 2.993, 4.926, 4.830, and 4.912 for Ba1, Ba2, Ga1, I1, I2, and I3 in 1, and 2.056, 1.792, 3.026, 5.026, 4.975, and 5.086 for Ba1, Ba2, Ga1, I1, I2, and I3 in 2,respectively.…”

“…[1][2][3][4][5][6] To the best of our knowledge,a ne xcellent second-order NLO material should feature al arge second harmonic generation (SHG) coefficient, ahigh relevant laserinduced damage threshold (LDT), appropriate optical transmittance range,m oderate birefringence for achieving phase matching,and good thermal stability.Inaddition, it should be free of moisture and accessible by af acile synthetic method. [7][8][9] Metal iodates currently attract extensive research interest due to their potential outstanding SHG response. [10] Up to now,several effective synthetic routes have been reported for exploring the NCS metal iodates featuring novel crystal structures and remarkable SHG performance,s uch as condensing IO 3 À and IO 4 3À units to form polyiodates, [11][12][13] combining six-or five-coordinate d 0 transition metal (TM) cations (e.g.T i 4+ ,V 5+ ,M o 6+ ,a nd Nb 5+ ) [14][15][16][17][18][19][20][21][22] or metal cations (e.g.…”

Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30 (M= Ca and Ba, RE= La and Bi)

“…2c). For Compound III, the K atoms bond to six or eight O atoms to form KO 6 the range of 1.310(2)-1.440(2) Å and the tetrahedral B atoms have longer B-O distances in the range of 1.437(18)-1.511(19) Å. The bond valence sums of all atoms in the title compounds are in a reasonable range according to the bond valence theory [67].…”

“…For Compounds I and II, the K atoms connect with six or eight O atoms to form KO 6 (Table S3). In the structure, similar to Compounds I and II, Compound III exhibits a complex 3D structure.…”

“…Nonlinear optical (NLO) materials have drawn considerable attention to date for their wide applications, such as material processing, information communication, and photochemical synthesis [1][2][3][4][5][6][7]. Numbers of famous NLO crystals have been obtained, including β-BaB 2 O 4 (β-BBO) [8], LiB 3 O 5 (LBO) [9], CsB 3 O 5 (CBO) [10], CsLiB 6 O 10 (CLBO) [11], KBe 2 BO 3 F 2 (KBBF) [12], Sr 2 Be 2 B 2 O 7 [13], K 2 Al 2 B 2 O 7 (KAB) [14], KTiOPO 4 (KTP) [15], KH 2 PO 4 (KDP) [16], AgGaQ 2 (Q = S, Se) [17,18], and ZnGeP 2 (ZGP) [19], which can expand the spectral ranges of solid state lasers from deep-ultraviolet (DUV) to infrared (IR).…”