Ba<sub>6</sub>Zn<sub>7</sub>Ga<sub>2</sub>S<sub>16</sub>: A Wide Band Gap Sulfide with Phase-Matchable Infrared NLO Properties
Yan-Yan Li
Peng-Fei Liu
Li-Ming Wu
10.1021/acs.chemmater.7b01321.s001
https://acs.figshare.com/articles/journal_contribution/Ba_sub_6_sub_Zn_sub_7_sub_Ga_sub_2_sub_S_sub_16_sub_A_Wide_Band_Gap_Sulfide_with_Phase-Matchable_Infrared_NLO_Properties/5099002
High-performance
infrared (IR) nonlinear optical (NLO) materials
with large laser damage thresholds (LDTs) are urgently needed because
the current commercially available AgGaS<sub>2</sub>, AgGaSe<sub>2</sub>, and ZnGeP<sub>2</sub> suffer their very low LDTs which shorten
significantly their service lifetimes. Here, a novel sulfide, Ba<sub>6</sub>Zn<sub>7</sub>Ga<sub>2</sub>S<sub>16</sub> with a very wide
band gap of 3.5 eV, has been discovered. This compound crystallizes
in the chiral trigonal <i>R</i>3 space group with a novel
3D framework that is constructed by ZnS<sub>4</sub> tetrahedra, Zn<sub>3</sub>GaS<sub>10</sub> supertetrahedra (a T2-type), and Zn<sub>3</sub>GaS<sub>10</sub> quadri-tetrahedral clusters via vertex-sharing.
Such a novel structure exhibits desirable features which suggest a
promising NLO material: phase-matchability (PM), good NLO efficiency
(about half that of benchmark AgGaS<sub>2</sub>), and the highest
LDT among PM chalcogenides (28 times that of benchmark AgGaS<sub>2</sub>). In addition, the density functional theory (DFT) calculations
confirm its PM behavior and reveal that the second harmonic generation
(SHG) origin is mainly ascribed to the transition process from S-3p
to Ga-4p, Zn-3p, Zn-3d, and Ba-5d states; the calculated <i>d</i><sub>11</sub> coefficient of 6.1 pm/V agrees well with experimental
values.
2017-05-31 00:00:00
benchmark AgGaS 2
band gap
R 3 space group
AgGaSe 2
T 2-type
Wide Band Gap Sulfide
AgGaS 2
11 coefficient
S -3p
LDT
Zn 3 GaS 10 supertetrahedra
compound crystallizes
PM behavior
SHG
NLO Properties High-performance
Ba 6 Zn 7 Ga 2 S 16
laser damage thresholds
ZnGeP 2
DFT
novel sulfide
transition process
novel structure exhibits
novel 3 D framework
service lifetimes
Ga -4p Zn -3p Zn -3d
NLO efficiency
Zn 3 GaS 10 quadri-tetrahedral clusters
ZnS 4 tetrahedra
IR
3.5 eV
Ba -5d states
NLO material