Ba2MAsQ5(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability

Abishek K. Iyer; Jeong Bin Cho; Michael J. Waters; Jun Sang Cho; Benjamin M. Oxley; James M. Rondinelli; Joon I. Jang; Mercouri G. Kanatzidis

doi:10.1021/acs.chemmater.2c00962

Ba₂MAsQ₅(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability

Abishek K. Iyer, Jeong Bin Cho, Michael J. Waters, Jun Sang Cho, Benjamin M. Oxley, James M. Rondinelli, Joon I. Jang^*, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	5283-5293
Number of pages	11
Journal	Chemistry of Materials
Volume	34
Issue number	11
DOIs	https://doi.org/10.1021/acs.chemmater.2c00962
State	Published - Jun 14 2022

Funding

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.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.2c00962

Cite this

@article{5aaf44fcfc864e608b43e68829c3ebb1,

title = "Ba2MAsQ5(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability",

abstract = "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.",

author = "Iyer, {Abishek K.} and Cho, {Jeong Bin} and Waters, {Michael J.} and Cho, {Jun Sang} and Oxley, {Benjamin M.} and Rondinelli, {James M.} and Jang, {Joon I.} and Kanatzidis, {Mercouri G.}",

note = "Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

year = "2022",

month = jun,

day = "14",

doi = "10.1021/acs.chemmater.2c00962",

language = "English (US)",

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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.

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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Ba₂MAsQ₅(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability

Abstract

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ASJC Scopus subject areas

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CSD 2162315: Experimental Crystal Structure Determination

CSD 2162317: Experimental Crystal Structure Determination

CSD 2162316: Experimental Crystal Structure Determination

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Ba2MAsQ5(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability

Abstract

Funding

ASJC Scopus subject areas

Access to Document

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Datasets

CSD 2162315: Experimental Crystal Structure Determination

CSD 2162317: Experimental Crystal Structure Determination

CSD 2162316: Experimental Crystal Structure Determination

Cite this

Ba₂MAsQ₅(Q = S and Se) Family of Polar Structures with Large Second Harmonic Generation and Phase Matchability