Second-harmonic generation (SHG)
response and birefringence are
two critically important properties of nonlinear optical (NLO) materials.
However, the simultaneous optimization of these two key properties
remains a major challenge because of their contrasting microstructure
requirements. Herein, we report the first tetravalent rare-earth metal
fluorinated sulfate, CeF2(SO4). Its structure
features novel net-like layers constructed by highly distorted [CeO4F4] polyhedra, which are further interconnected
by [SO4] tetrahedra to form a three-dimensional structure.
CeF2(SO4) exhibits the strongest SHG effect
(8 times that of KH2PO4) and the largest birefringence
for sulfate-based NLO materials, the latter exceeding the birefringent
limit for oxides. Theoretical calculations and crystal structure analysis
reveal that the unusually large SHG response and giant birefringence
can be attributed to the introduction of the highly polarizable fluorinated
[CeO4F4] polyhedra as well as the favorable
alignment of [CeO4F4] polyhedra and [SO4] tetrahedra. This research affords a new paradigm for the
designed synthesis of high-performance NLO materials.
Wide ultraviolet (UV) transparency, strong second‐harmonic generation (SHG) response, and sufficient optical birefringence for phase‐matching (PM) at short SHG wavelengths are vital for practical UV nonlinear optical (NLO) materials. However, simultaneously optimizing these properties is a major challenge, particularly for metal phosphates. Herein, we report a non‐traditional π‐conjugated cation‐based UV NLO phosphate [C(NH2)3]6(PO4)2⋅3 H2O (GPO) with a short UV cutoff edge. GPO is SHG active at 1064 nm (3.8 × KH2PO4 @ 1064 nm) and 532 nm (0.3 × β‐BaB2O4 @ 532 nm) and also possesses a significant birefringence (0.078 @ 546 nm) with a band gap >6.0 eV. The PM SHG capability of GPO can extend to 250 nm, indicating GPO is a promising UV solar‐blind NLO material. Calculations and crystal structure analysis show that the rare coexistence of wide UV transparency, large SHG response, and optical anisotropy is due to the introduction of π‐conjugated cations [C(NH2)3]+ and their favorable arrangement with [PO4]3− anions.
Second-harmonic-generation (SHG)
efficiency and birefringence are
two crucial parameters for nonlinear optical (NLO) crystals. However,
the simultaneous optimization of these two key parameters remains
a great challenge due to their contrasting microstructure prerequisites.
In this paper, the first example of tetravalent rare-earth iodate-sulfate
Ce(IO3)2(SO4) (CISO) was designed
by a defluorinated homovalent substitution strategy based on the parent
compound CeF2(SO4)·H2O (CFSO)
from the centrosymmetric to the noncentrosymmetric structure, which
shows a large SHG effect of 3.5 × KDP in metal sulfates and a
significant birefringence (0.259 at 546 nm) in hetero-oxyanion tetrahedral-group-based
optical crystals. In the structure of CISO, both [IO3]
and [SO4] groups are in the cis-position
to each other, while [CeO8] polyhedra are highly distorted
due to the different coordination environments of two kinds of oxyanions
in one structure, which displays optimized optical anisotropy and
polarizability attributed to their synergistic effect, leading to
the strong SHG efficiency and sufficient birefringence. First-principles
simulations for CISO have been employed to rationalize the correlations
between the molecular structure and optical properties.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.