TY - JOUR
T1 - Why Some Noncentrosymmetric Borates Do Not Make Good Nonlinear Optical Materials
T2 - A Case Study with K3B5O8(OH)2
AU - Ding, Fenghua
AU - Nisbet, Matthew L.
AU - Zhang, Weiguo
AU - Halasyamani, P. Shiv
AU - Chai, Liyuan
AU - Poeppelmeier, Kenneth R.
N1 - Funding Information:
Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. W.Z. and P.S.H. thank the Welch Foundation (E-1457) and the NSF (DMR-1503573) for support.
Funding Information:
This work was supported by funding from the National Science Foundation (DMR-1608218) and a scholarship from the China Scholarship Council (F.D.). The single-crystal X-ray data and FT-IR measurements were acquired at Northwestern University’s Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which is supported by grants from NSF-NSEC, NSF-MRSEC, the KECK Foundation, the State of Illinois, and Northwestern University. This work made use of the J. B.
PY - 2018/9/17
Y1 - 2018/9/17
N2 - Synthesis of deep-ultraviolet (DUV) transparent materials, especially those with noncentrosymmetric structures, remains a great challenge in the solid-state chemistry community. A new DUV transparent borate, K3B5O8(OH)2, was discovered with a short absorption edge below 200 nm. The title compound crystallizes in a noncentrosymmetric, polar space group, Fdd2 (point group mm2), with the following cell parameters: a = 13.736(9) Å, b = 19.317(12) Å, c = 7.606(5) Å. The structure of K3B5O8(OH)2 features a 3D framework composed of [B5O8(OH)2]3- basic building units that are linked by contacts with K+ cations and O-H···O hydrogen bonds. Second harmonic generation (SHG) measurements were performed, and an SHG efficiency of 0.5 × SiO2 was observed. Symmetry dictates that the 14 component of the macroscopic NLO susceptibility is equal to zero in mm2, which prevents the maximal component of the microscopic NLO susceptibility for [B5O8(OH)2]3- units (14) from contributing to the macroscopic NLO susceptibility of the crystal and therefore limits the SHG efficiency. In contrast, large SHG effects can be observed from compounds containing [B5O10] units that crystallize in point groups with nonzero 14, such as 222. These findings provide insight into understanding the relationship between crystal structure and SHG efficiency in [B5O10]-based compounds and discovering other borate-based DUV materials.
AB - Synthesis of deep-ultraviolet (DUV) transparent materials, especially those with noncentrosymmetric structures, remains a great challenge in the solid-state chemistry community. A new DUV transparent borate, K3B5O8(OH)2, was discovered with a short absorption edge below 200 nm. The title compound crystallizes in a noncentrosymmetric, polar space group, Fdd2 (point group mm2), with the following cell parameters: a = 13.736(9) Å, b = 19.317(12) Å, c = 7.606(5) Å. The structure of K3B5O8(OH)2 features a 3D framework composed of [B5O8(OH)2]3- basic building units that are linked by contacts with K+ cations and O-H···O hydrogen bonds. Second harmonic generation (SHG) measurements were performed, and an SHG efficiency of 0.5 × SiO2 was observed. Symmetry dictates that the 14 component of the macroscopic NLO susceptibility is equal to zero in mm2, which prevents the maximal component of the microscopic NLO susceptibility for [B5O8(OH)2]3- units (14) from contributing to the macroscopic NLO susceptibility of the crystal and therefore limits the SHG efficiency. In contrast, large SHG effects can be observed from compounds containing [B5O10] units that crystallize in point groups with nonzero 14, such as 222. These findings provide insight into understanding the relationship between crystal structure and SHG efficiency in [B5O10]-based compounds and discovering other borate-based DUV materials.
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U2 - 10.1021/acs.inorgchem.8b01965
DO - 10.1021/acs.inorgchem.8b01965
M3 - Article
C2 - 30168320
AN - SCOPUS:85052859855
VL - 57
SP - 11801
EP - 11808
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 18
ER -