Synthesis, crystal and electronic structures, linear and nonlinear optical properties, and photocurrent response of oxyhalides CeHaVIO$_4$ (Ha = Cl, Br; VI = Mo, W)
Jiao, Zixian Quah, Jasmine Syed, Tajamul Hussain Wei, Wei Zhang, Bingbing Wang, Fei Wang, Jian
Jiao, Zixian
Quah, Jasmine
Syed, Tajamul Hussain
Wei, Wei
Zhang, Bingbing
Wang, Fei
Wang, Jian
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2023-12
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Article
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Keywords
Bromine compounds,Cerium compounds,Charge transfer,Crystal structure,Electronic structure,Energy gap,Harmonic generation,Lanthanum compounds,Molybdenum compounds,Nonlinear optics,Optical properties,Phase matching,Photocurrents,Single crystals,Tungsten compounds
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Citation
Jiao, Z., Quah, J., Syed, T.H., Wei, W., Zhang, B., Wang, F., & Wang, J. (2023). Synthesis, crystal and electronic structures, linear and nonlinear optical properties, and photocurrent response of oxyhalides CeHaVIO$_4$ (Ha = Cl, Br; VI = Mo, W). Dalton Transactions. https://doi.org/10.1039/D3DT03640E
Abstract
Four heteroanionic oxyhalides, CeClMoO$_4$, CeBrMoO$_4$, CeClWO$_4$, and CeBrWO$_4$, have been studied as multifunctional materials, which show a combination of good second harmonic generation (SHG) response and photocurrent signals. Millimeter-sized CeHaVIO$_4$ (Ha = Cl, Br; VI = Mo, W) crystals were grown by halide salt flux. The crystal structure of CeHaVIO$_4$ crystals was accurately determined by single-crystal X-ray diffraction. CeClMoO$_4$, CeBrMoO$_4$, and CeBrWO$_4$ are isostructural to each other, and crystallize in the acentric LaBrMoO4 structure type. CeClWO$_4$ crystallizes in a new structure type with unit cell parameters of $a$ = 19.6059(2) Å, $b$ = 5.89450(10) Å, $c$ = 7.80090(10) Å, and β = 101.4746(8)°. The bandgaps of CeHaVIO$_4$ fall into the range of 2.8(1)-3.1(1) eV, which are much smaller than those of isotypic LaHaVIO$_4$ (Ha = Cl, Br; VI = Mo, W) in the range of 3.9(1)-4.3(1) eV. The narrowing of bandgaps in CeHaVIO$_4$ originates from the presence of partially filled 4f orbitals of cerium atoms, which was confirmed by density functional theory (DFT) calculations. The moderate bandgaps make CeHaVIO$_4$ suitable for infrared nonlinear optical (IR NLO) applications. CeBrMoO$_4$ and CeBrWO$_4$ exhibit moderate SHG responses of 0.58x AGS and 0.46x AGS, respectively, and are both type-I phase-matching materials. Moderate SHG response, easy growth of crystals, high ambient stability, and type-I phase-matching behavior make CeBrMoO$_4$ and CeBrWO$_4$ great materials for IR NLO applications. CeHaVIO$_4$ films also exhibited good photocurrent response upon light radiation. This work demonstrates the rich structural chemistry of the REHaVIO$_4$ (RE = Y, La-Lu; Ha = Cl, Br; VI = Mo, W) family and the potential presence of more multifunctional materials.
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Royal Society of Chemistry
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Dalton Transactions
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1477-9226