Journal
INORGANIC CHEMISTRY
Volume 60, Issue 10, Pages 7553-7560Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c01052
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Funding
- National Natural Science Foundation of China [21975255, 51890862, 21921001, U1605245]
- National Key Research and Development Plan of Ministry of Science and Technology [2016YFB0402104]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000]
- NSF of Fujian Province [2019J01020758]
- Youth Innovation Promotion Association CAS [2019303]
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Two polymorphic phosphide-based infrared non-linear optical crystals, alpha-Ca2CdP2 and beta-Ca2CdP2, show strong SHG intensities and suitable optical properties, indicating their potential as IR NLO materials.
Two polymorphic phosphide-based infrared (IR) non-linear optical (NLO) crystals, alpha-Ca2CdP2 and beta-Ca2CdP2, were obtained by combining alkaline-earth metals and d(10) transition metals using metal flux and metal salt flux methods, respectively. The crystal structure of alpha-Ca2CdP2 is orthorhombic in the space group Cmc2(1) (no. 36), while the structure of beta-Ca2CdP2 is monoclinic in the space group Cm (no. 8). Both are two-dimensional layered structures that are composed of CdP4 tetrahedra layers via sharing vertices, which stack along the b-axis and the c-axis, respectively. The second harmonic generation (SHG) measurements manifest that alpha-Ca2CdP2 and beta Ca2CdP2 exhibit strong SHG intensities (1.41 and 3.28 x that of AgGaS2 at a 2050 nm laser, respectively). Other optical measurements indicate that alpha-Ca2CdP2 and beta-Ca2CdP2 have suitable band gaps (1.98 and 1.55 eV, respectively), high laser-induced damage thresholds (4.5 and 3.1x that of AgGaS2 at 1064 nm laser, respectively) and appropriate birefringence (0.12 and 0.20 at 2050 nm, respectively) in addition to covering wide infrared transparent regions. The research on alpha-Ca2CdP2 and beta-Ca2CdP2 demonstrates that they are potential IR NLO candidates. Theoretical calculations uncover that their SHG effects are from distorted CdP4 tetrahedra, highlighting that tetrahedral motifs, including d(10) transition metals, would be ideal NLO-active building blocks.
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