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Title: Soluble semiconductors AAsSe{sub 2} (A = Li, Na) with a direct-band-gap and strong second harmonic generation : a combined experimental and theoretical study.

Abstract

AAsSe{sub 2} (A = Li, Na) have been identified as a new class of polar direct-band gap semiconductors. These I-V-VI{sub 2} ternary alkali-metal chalcoarsenates have infinite single chains of (1/{infinity})[AsQ{sub 2}{sup -}] derived from corner-sharing pyramidal AsQ{sup 3} units with stereochemically active lone pairs of electrons on arsenic. The conformations and packing of the chains depend on the structure-directing alkali metals. This results in at least four different structural types for the Li1-xNaxAsSe{sub 2} stoichoimetry ({alpha}-LiAsSe{sub 2}, {beta}-LiAsSe{sub 2}, {gamma}-NaAsSe{sub 2}, and {delta}-NaAsSe{sub 2}). Single-crystal X-ray diffraction studies showed an average cubic NaCl-type structure for {alpha}-LiAsSe{sub 2}, which was further demonstrated to be locally distorted by pair distribution function (PDF) analysis. The {beta} and {gamma} forms have polar structures built of different (1/{infinity})[AsSe{sub 2}{sup -}] chain conformations, whereas the {delta} form has nonpolar packing. A wide range of direct band gaps are observed, depending on composition: namely, 1.11 eV for {alpha}-LiAsSe{sub 2}, 1.60 eV for LiAsS{sub 2}, 1.75 eV for {gamma}-NaAsSe{sub 2}, 2.23 eV for NaAsS{sub 2}. The AAsQ{sub 2} materials are soluble in common solvents such as methanol, which makes them promising candidates for solution processing. Band structure calculations performed with the highly precise screened-exchange sX-LDA FLAPW method confirmmore » the direct-gap nature and agree well with experiment. The polar {gamma}-NaAsSe{sub 2} shows very large nonlinear optical (NLO) second harmonic generation (SHG) response in the wavelength range of 600-950 nm. The theoretical studies confirm the experimental results and show that {gamma}-NaAsSe{sub 2} has the highest static SHG coefficient known to date, 337.9 pm/V, among materials with band gaps larger than 1.0 eV.« less

Authors:
; ; ; ; ; ;  [1]
  1. Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1008298
Report Number(s):
ANL/MSD/JA-69074
Journal ID: 0002-7863; TRN: US201106%%386
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.
Additional Journal Information:
Journal Volume: 132; Journal Issue: Feb. 19, 2010
Country of Publication:
United States
Language:
ENGLISH
Subject:
10 SYNTHETIC FUELS; ALKALI METALS; ARSENIC; CHAINS; DISTRIBUTION FUNCTIONS; ELECTRONS; HARMONIC GENERATION; METHANOL; PROCESSING; SOLVENTS; WAVELENGTHS; X-RAY DIFFRACTION

Citation Formats

Bera, T K, Jang, J I, Song, J-H, Malliakas, C D, Freeman, A J, Ketterson, J B, Kanatzidis, M G, and Northwestern Univ.). Soluble semiconductors AAsSe{sub 2} (A = Li, Na) with a direct-band-gap and strong second harmonic generation : a combined experimental and theoretical study.. United States: N. p., 2010. Web. doi:10.1021/ja9094846.
Bera, T K, Jang, J I, Song, J-H, Malliakas, C D, Freeman, A J, Ketterson, J B, Kanatzidis, M G, & Northwestern Univ.). Soluble semiconductors AAsSe{sub 2} (A = Li, Na) with a direct-band-gap and strong second harmonic generation : a combined experimental and theoretical study.. United States. https://doi.org/10.1021/ja9094846
Bera, T K, Jang, J I, Song, J-H, Malliakas, C D, Freeman, A J, Ketterson, J B, Kanatzidis, M G, and Northwestern Univ.). 2010. "Soluble semiconductors AAsSe{sub 2} (A = Li, Na) with a direct-band-gap and strong second harmonic generation : a combined experimental and theoretical study.". United States. https://doi.org/10.1021/ja9094846.
@article{osti_1008298,
title = {Soluble semiconductors AAsSe{sub 2} (A = Li, Na) with a direct-band-gap and strong second harmonic generation : a combined experimental and theoretical study.},
author = {Bera, T K and Jang, J I and Song, J-H and Malliakas, C D and Freeman, A J and Ketterson, J B and Kanatzidis, M G and Northwestern Univ.)},
abstractNote = {AAsSe{sub 2} (A = Li, Na) have been identified as a new class of polar direct-band gap semiconductors. These I-V-VI{sub 2} ternary alkali-metal chalcoarsenates have infinite single chains of (1/{infinity})[AsQ{sub 2}{sup -}] derived from corner-sharing pyramidal AsQ{sup 3} units with stereochemically active lone pairs of electrons on arsenic. The conformations and packing of the chains depend on the structure-directing alkali metals. This results in at least four different structural types for the Li1-xNaxAsSe{sub 2} stoichoimetry ({alpha}-LiAsSe{sub 2}, {beta}-LiAsSe{sub 2}, {gamma}-NaAsSe{sub 2}, and {delta}-NaAsSe{sub 2}). Single-crystal X-ray diffraction studies showed an average cubic NaCl-type structure for {alpha}-LiAsSe{sub 2}, which was further demonstrated to be locally distorted by pair distribution function (PDF) analysis. The {beta} and {gamma} forms have polar structures built of different (1/{infinity})[AsSe{sub 2}{sup -}] chain conformations, whereas the {delta} form has nonpolar packing. A wide range of direct band gaps are observed, depending on composition: namely, 1.11 eV for {alpha}-LiAsSe{sub 2}, 1.60 eV for LiAsS{sub 2}, 1.75 eV for {gamma}-NaAsSe{sub 2}, 2.23 eV for NaAsS{sub 2}. The AAsQ{sub 2} materials are soluble in common solvents such as methanol, which makes them promising candidates for solution processing. Band structure calculations performed with the highly precise screened-exchange sX-LDA FLAPW method confirm the direct-gap nature and agree well with experiment. The polar {gamma}-NaAsSe{sub 2} shows very large nonlinear optical (NLO) second harmonic generation (SHG) response in the wavelength range of 600-950 nm. The theoretical studies confirm the experimental results and show that {gamma}-NaAsSe{sub 2} has the highest static SHG coefficient known to date, 337.9 pm/V, among materials with band gaps larger than 1.0 eV.},
doi = {10.1021/ja9094846},
url = {https://www.osti.gov/biblio/1008298}, journal = {J. Am. Chem. Soc.},
number = Feb. 19, 2010,
volume = 132,
place = {United States},
year = {Fri Feb 19 00:00:00 EST 2010},
month = {Fri Feb 19 00:00:00 EST 2010}
}