TY - JOUR
T1 - Ba2MAsQ5(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability
AU - Iyer, Abishek K.
AU - Cho, Jeong Bin
AU - Waters, Michael J.
AU - Cho, Jun Sang
AU - Oxley, Benjamin M.
AU - Rondinelli, James M.
AU - Jang, Joon I.
AU - Kanatzidis, Mercouri G.
N1 - Funding Information:
M.G.K., A.K.I, and B.M.O. acknowledge the Air Force Office of Scientific Research Grant Number FA9550-18-S-0003. The IMSERC PCM facility at Northwestern University used in this work received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University. The computational work by J.M.R and M.J.W. was supported by the National Science Foundation (NSF) Grant No. DMR-2011208. Access to facilities for high-performance computing resources at Northwestern University is acknowledged. J.I.J. acknowledges the support of the Basic Science Research Programs (2020R1F1A1069646 and 2021R1A2C2013625) through the National Research Foundation of Korea (NRF), funded by the Korean government. M.J.W. would like to thank Anubhab Haldar for his performance enhancing patches to GPAW.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/6/14
Y1 - 2022/6/14
N2 - Noncentrosymmetric chalcogenides containing stereochemically active lone pair elements, such as As, Sb, and Bi, offer a useful way to tune the band gap and enhance the second harmonic generation (SHG) response. Ba2As2-xSbxQ5, Ba2As2-xBixQ5 (Q = S and Se), and Ba2As2S4.8Se0.2 are new chalcoarsenates that crystallize in the noncentrosymmetric monoclinic space group P21. These five new compounds crystallized with a three-dimensional (3D) Ba2As2Se5-type structure, containing AsQ3 units and [As2Q4]2- dimeric units. The [As2Q4]2- dimeric unit can be tuned by replacing As with Sb or Bi and Se with S. In contrast, Ba2As2S5 crystallizes in the orthorhombic space group Pca21. Differential thermal analysis suggested that Ba2As2S5, Ba2As2Se5, Ba2AsSbSe5, and Ba2As1.25Bi0.75Se5 melt congruently. The [M2Q4]2- unit plays a significant role in tuning the band gap of these compounds, decreasing from 2.02 eV in Ba2As2S5 to 1.37 eV in Ba2As1.25Bi0.75Se5. Powder SHG measurements showed all the compounds are essentially phase-matchable at 3300 nm. Ba2AsSbSe5 exhibits the highest χ(2) of 36 pm/V and a laser-induced damage threshold of 0.10 GW/cm2, comparable to that of AgGaQ2. These materials show significantly improved SHG behavior response to BaGa4Q7 compounds, making them attractive for commercial applications.
AB - Noncentrosymmetric chalcogenides containing stereochemically active lone pair elements, such as As, Sb, and Bi, offer a useful way to tune the band gap and enhance the second harmonic generation (SHG) response. Ba2As2-xSbxQ5, Ba2As2-xBixQ5 (Q = S and Se), and Ba2As2S4.8Se0.2 are new chalcoarsenates that crystallize in the noncentrosymmetric monoclinic space group P21. These five new compounds crystallized with a three-dimensional (3D) Ba2As2Se5-type structure, containing AsQ3 units and [As2Q4]2- dimeric units. The [As2Q4]2- dimeric unit can be tuned by replacing As with Sb or Bi and Se with S. In contrast, Ba2As2S5 crystallizes in the orthorhombic space group Pca21. Differential thermal analysis suggested that Ba2As2S5, Ba2As2Se5, Ba2AsSbSe5, and Ba2As1.25Bi0.75Se5 melt congruently. The [M2Q4]2- unit plays a significant role in tuning the band gap of these compounds, decreasing from 2.02 eV in Ba2As2S5 to 1.37 eV in Ba2As1.25Bi0.75Se5. Powder SHG measurements showed all the compounds are essentially phase-matchable at 3300 nm. Ba2AsSbSe5 exhibits the highest χ(2) of 36 pm/V and a laser-induced damage threshold of 0.10 GW/cm2, comparable to that of AgGaQ2. These materials show significantly improved SHG behavior response to BaGa4Q7 compounds, making them attractive for commercial applications.
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U2 - 10.1021/acs.chemmater.2c00962
DO - 10.1021/acs.chemmater.2c00962
M3 - Article
AN - SCOPUS:85131670336
VL - 34
SP - 5283
EP - 5293
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 11
ER -