Synthesis, Characterization and Property of a New UV Nonlinear Optical Crystal KNa5Ca5(CO3)8

doi:10.15541/jim20170335

Abstract

Abstract:

A new carbonate nonlinear optical (NLO) material, KNa₅Ca₅(CO₃)₈, was successfully synthesized by mild hydrothermal method. It crystallizes in hexagonal space group (P63mc) with lattice parameters a=b=1.00786(4) and c=1.26256(8) nm (Z=2). Structure of KNa₅Ca₅(CO₃)₈ can be described as standing-on-edge [CO₃] groups connecting the adjacent inﬁnite [CaCO₃]_∞ layers in the a-b plane to construct a framework with four types of channels running parallel to [010]. K, Na and [Na_0.67Ca_0.33] atoms reside in the tunnels. In the structure, the ?at-lying [CO₃] groups in two successive layers present an opposite orientation. This arrangement is negative for NLO susceptibilities. The macroscopic of SHG effects, however, originated from the standing-on-edge [CO₃] group along c axis. It is regrettable that the standing-on-edge [C3O₃] and [C4O₃] groups are almost arranged oppositely to the c direction, which weakens the SHG contribution from the standing-on-edge [CO₃] groups. Measurement of second harmonic generation (SHG) by the method adapted from Kurtz and Perry indicates that the compound is phase-matchable in visible region and exhibit moderate SHG response about 1.2 times higher than that of KH₂PO₄. In addition, UV-Vis-NIR diffuse reflectance spectral measurements indicate that KNa₅Ca₅(CO₃)₈ has a large optical gap about 5.95 eV. Moreover, first-principles electronic structure calculations show that the CO₃ groups play an important role in the total SHG response. Therefore, our data suggests that the new compound as NLO material may have potential applications in the UV region.

Key words: UV, carbonates, nonlinear optical crystal, crystal growth

CLC Number:

TQ174

CHEN Qiao-Ling, LUO Min, LIN Chen-Sheng. Synthesis, Characterization and Property of a New UV Nonlinear Optical Crystal KNa₅Ca₅(CO₃)₈[J]. Journal of Inorganic Materials, 2018, 33(6): 667-672.

Figures/Tables 9

References 34

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Formula	KNa₅Ca₅(CO₃)₈
Formula mass/amu	834.53
Crystal system	Hexagonal
Space group	P63 mc
a/nm	1.00786(4)
c/nm	1.26256(8)
α/(°)	90
γ/(°)	120
V/nm³	1.11066(9)
Z	2
ρ(calcd)(g/cm³)	2.495
Temperature/K	293(2)
λ/nm	0.071073
F (000)	828
μ/mm^-1	3.600
θ/(°)	2.33-27.50
Rint	0.0304
R/wR (I>2σ (I))	0.0620/0.1706
R/wR (all data)	0.0624/0.1710
GOF on F2	1.083
Largest Diff. peak and hole (e/nm^-3)	0.900 and-0.000574

Formula	KNa₅Ca₅(CO₃)₈
Formula mass/amu	834.53
Crystal system	Hexagonal
Space group	P63 mc
a/nm	1.00786(4)
c/nm	1.26256(8)
α/(°)	90
γ/(°)	120
V/nm³	1.11066(9)
Z	2
ρ(calcd)(g/cm³)	2.495
Temperature/K	293(2)
λ/nm	0.071073
F (000)	828
μ/mm^-1	3.600
θ/(°)	2.33-27.50
Rint	0.0304
R/wR (I>2σ (I))	0.0620/0.1706
R/wR (all data)	0.0624/0.1710
GOF on F2	1.083
Largest Diff. peak and hole (e/nm^-3)	0.900 and-0.000574

Crystal	Band gap/ eV	Nonlinear optical effect (×KDP)	Angle between CO₃group and c axis/(°)
KNa₅Ca₅(CO₃)₈	5.95	1.2	18.92
CsNa₅Ca₅(CO₃)₈	5.92	1.0	16.00

Crystal	Band gap/ eV	Nonlinear optical effect (×KDP)	Angle between CO₃group and c axis/(°)
KNa₅Ca₅(CO₃)₈	5.95	1.2	18.92
CsNa₅Ca₅(CO₃)₈	5.92	1.0	16.00

Synthesis, Characterization and Property of a New UV Nonlinear Optical Crystal KNa₅Ca₅(CO₃)₈

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