New Ultraviolet Nonlinear Optical Crystal Rb3Hg2(SO4)3Cl

doi:10.15541/jim20220667

Abstract

Abstract:

Ultraviolet (UV) nonlinear optical (NLO) crystals play an irreplaceable role as the key materials to realize the frequency conversion for all solid state lasers. To date, it is still difficult to design UV NLO crystals with large second harmonic generation (SHG) coefficients, moderate birefringences and wide band gaps. Benefiting from the large band gap, sulfate has become an important research direction of UV NLO crystals. However, since SO₄ is isotropic tetrahedral building units with nearly nonpolar T_d symmetry, it exhibits small microscopic second order polarizability and polarizability anisotropy, which tends to result in a weak SHG effect and small birefringence. In this work, we introduced Hg²⁺ ions that are easy to form distorted polyhedrons into the sulfates, resulting in a new NLO material, Rb₃Hg₂(SO₄)₃Cl. It crystallizes in a monoclinic space group (P2₁) with the lattice parameters a=0.78653(2) nm, b=0.97901(2) nm, c=1.00104(3) nm, and β=110.95(3) (Z=2). Structure of Rb₃Hg₂(SO₄)₃Cl consists of [SO₄] tetrahedra, [HgO₅] and [HgO₄Cl] polyhedral, which connected by a common corner to form a spatial 3D network. All the Rb atoms reside in the cavity of 3D network. The powder SHG measurement proposed by Kurtz and Perry indicates that Rb₃Hg₂(SO₄)₃Cl is a phase-matchable material in the visible region and exhibits a moderate SHG response about 1.5 times that of KH₂PO₄ (KDP). In addition, the UV-Vis-NIR diffuse reflectance spectral measurement indicates that Rb₃Hg₂(SO₄)₃Cl has a short UV cut-off edge of 251 nm, corresponding to the band gap of 4.94 eV. Its polarizing microscope measurement reveals that Rb₃Hg₂(SO₄)₃Cl has a moderate birefringence (The birefringence of Rb₃Hg₂(SO₄)₃Cl crystal at 546.1 nm is 0.04). Moreover, first-principles calculations uncover that the distorted [HgO₅], [HgO₄Cl] and [SO₄] polyhedral are responsible for its SHG effect. Our study shows that Rb₃Hg₂(SO₄)₃Cl may have potential applications as a UV NLO crystal.

Key words: ultraviolet, Hg-based sulfate, nonlinear optical crystal, crystal structure

CLC Number:

TQ174

SONG Yunxia, HAN Yinglei, YAN Tao, LUO Min. New Ultraviolet Nonlinear Optical Crystal Rb₃Hg₂(SO₄)₃Cl[J]. Journal of Inorganic Materials, 2023, 38(7): 778-784.

Figures/Tables 13

Fig. 1 XRD pattern of (a) Rb3Hg2(SO4)3Cl and its crystal data fitting results (b)

Fig. 2 Energy dispersive X-ray spectrum of Rb3Hg2(SO4)3Cl

Fig. 3 TG curve of Rb3Hg2(SO4)3Cl

Table 1 Crystal parameters and structure refinements for Rb3Hg2(SO4)3Cl

Parameters	Rb₃Hg₂(SO₄)₃Cl
Mass formula	981.22
Crystal system	Monoclinic
Space group	P2₁
a/nm	0.78653(2)
b/nm	0.97901(2)
c/nm	1.00104(3)
β/(°)	111.095(3)
V/nm³	0.71916(3)
Z	2
ρ(calcd)/(g·cm^-3)	4.531
Temperature/K	293(2)
λ/nm	0.071073
F(000)	864.0
μ/mm^-1	39.701
Rint	0.0304
R/wR (I>2σ(I))	0.0304/0.0703
R/wR (all data)	0.0317/0.0712
GOF on F²	1.023
Largest diff. peak and hole (e/nm^-3)	1.22×10^-3 and -1.76×10^-3

Fig. 4 Crystal structure of Rb3Hg2(SO4)3Cl (a) Coordination environment of S and Hg ions; (b) Stacking of [SO4], [HgO5] and [HgO4Cl] polyhedra within a single cell; (c) Spatial network structure

Fig. 5 UV-Vis-NIR diffuse reflectance spectrum of Rb3Hg2(SO4)3Cl

Fig. 6 Images of Rb3Hg2(SO4)3Cl birefringence (a) Crystals in polarized light; (b) Completed extinction of the crystal with forward compensation; (c) Completed extinction of the crystal with reverse compensation; (d) Thickness of measured crystal

Fig. 7 SHG measurements of Rb3Hg2(SO4)3Cl ground crystals (red) with KDP (black) as a reference

Table 2 Calculated dipole moments of Rb3Hg2(SO4)3Cl

Species	Dipole moment/D
Species	x	y	z	Total
HgO₅(typeⅠ)	1.277	0.673	-0.563	1.549
HgO₅(typeⅡ)	-1.277	0.673	0.563	1.549
∑_Hg-O	0	1.346	0	1.346
HgO₄Cl(typeⅠ)	0.270	3.231	-1.591	3.611
HgO₄Cl(typeⅡ)	-0.262	3.224	1.591	3.605
∑_Hg-O& ∑_Hg-Cl	0.008	6.455	0	6.455
SO₄(typeⅠ)	-0.928	-0.103	2.047	2.250
SO₄(typeⅡ)	-1.177	1.609	0.607	2.084
SO₄(typeⅢ)	1.767	-0.702	-1.505	2.425
SO₄(typeⅣ)	0.928	-0.102	-2.039	2.243
SO₄(typeⅤ)	-1.765	-0.702	1.512	2.428
SO₄(typeⅥ)	1.176	1.611	-0.608	2.085
∑_S-O	0.001	1.611	0.014	1.611

Fig. 8 Energy band structures and electronic density distribution of Rb3Hg2(SO4)3Cl (a) Diagram of calculated electronic band structures; (b) Diagrams of calculated PDOS

Fig. 9 Calculated electron density diagram of Rb3Hg2(SO4)3Cl

Fig. 10 Calculated SHG coefficients of Rb3Hg2(SO4)3Cl

Fig. 11 Calculated refractive index dispersion curves of Rb3Hg2(SO4)3Cl

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New Ultraviolet Nonlinear Optical Crystal Rb₃Hg₂(SO₄)₃Cl

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