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        Optical Nonlinearity in Cu<sub>2</sub>CdSnS<sub>4</sub> and α/β-Cu<sub>2</sub>ZnSiS<sub>4</sub>: Diamond-like Semiconductors with High Laser-Damage Thresholds

        Rosmus, Kimberly A.,Brant, Jacilynn A.,Wisneski, Stephen D.,Clark, Daniel J.,Kim, Yong Soo,Jang, Joon I.,Brunetta, Carl D.,Zhang, Jian-Han,Srnec, Matthew N.,Aitken, Jennifer A. American Chemical Society 2014 Inorganic Chemistry Vol.53 No.15

        <P>Cu<SUB>2</SUB>CdSnS<SUB>4</SUB> and α/β-Cu<SUB>2</SUB>ZnSiS<SUB>4</SUB> meet several criteria for promising nonlinear optical materials for use in the infrared (IR) region. Both are air-stable, crystallize in noncentrosymmetric space groups, and possess high thermal stabilities. Cu<SUB>2</SUB>CdSnS<SUB>4</SUB> and α/β-Cu<SUB>2</SUB>ZnSiS<SUB>4</SUB> display wide ranges of optical transparency, 1.4–25 and 0.7–25 μm, respectively, and have relatively large second-order nonlinearity as well as phase matchability for wide regions in the IR. The laser-damage threshold (LDT) for Cu<SUB>2</SUB>CdSnS<SUB>4</SUB> is 0.2 GW/cm<SUP>2</SUP>, whereas α/β-Cu<SUB>2</SUB>ZnSiS<SUB>4</SUB> has a LDT of 2.0 GW/cm<SUP>2</SUP> for picosecond near-IR excitation. Both compounds also exhibit efficient third-order nonlinearity. Electronic structure calculations provide insight into the variation in properties.</P><P>Changing Sn<SUP>4+</SUP> to Si<SUP>4+</SUP> in the I<SUB>2</SUB>−II−IV−VI<SUB>4</SUB> formula has significant effects on the characteristics critical for nonlinear optical applications. The air-stable, noncentrosymmetric, diamond-like Cu<SUB>2</SUB>CdSnS<SUB>4</SUB> and α/β-Cu<SUB>2</SUB>ZnSiS<SUB>4</SUB> exhibit significant second- and third-order nonlinearity. These materials are practical for applications because of their elevated thermal stabilities, wide optical transparency windows, broad regions of phase matchability for second harmonic generation, and high laser-damage thresholds (LDTs). The LDT of the wide-gap α/β-Cu<SUB>2</SUB>ZnSiS<SUB>4</SUB> surpasses that of commercially available materials.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2014/inocaj.2014.53.issue-15/ic501310d/production/images/medium/ic-2014-01310d_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic501310d'>ACS Electronic Supporting Info</A></P>

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