Lead-strontium borate halides with hilgardite-type structure and their SHG properties

B. V. Egorova, A. V. Olenev, P. S. Berdonosov, A. N. Kuznetsov, S. Yu. Stefanovich, V. A. Dolgikh, T. Mahenthirarajah, P. Lightfoot

Research output: Contribution to journalArticlepeer-review

52 Citations (Scopus)

Abstract

Lead-containing members of the hilgardite family of borate halides, M2B5O9X (M = Ca, Sr, Ba, Pb; X = Cl, Br) exhibit an abnormally large nonlinear optical response. In order to establish any underlying crystal-chemical rationale for this we have carried out detailed crystallographic characterisations of the representative members of this series, Sr(2)b(5)O(9)Cl and Pb2B5O9Cl, using powder neutron diffraction. Both adopt the orthorhombic hilgardite structure type, in space group Pnn2. The full solid solution range Pb2-xSrxB5O9Cl has also been prepared, and studied by X-ray Rietveld and second harmonic generation (SHG) measurements. The SHG response shows a linear decrease with increasing x, whereas the unit cell shows an increasing orthorhombic distortion. However, the crystallographic results suggest no significant or systematic changes in the nature of the borate sublattice between Sr2B5O9Cl and Pb2B5O9Cl. We conclude that the enhanced SHG response in Pb-containing hilgardites is due predominantly to the presence of the polarizable nature of Pb2+, in particular the presence of a stereochemically active lone pair. (C) 2008 Elsevier Inc. All rights reserved.

Original languageEnglish
Pages (from-to)1891-1898
Number of pages8
JournalJournal of Solid State Chemistry
Volume181
DOIs
Publication statusPublished - Aug 2008

Keywords

  • borates
  • hilgardite
  • nonlinear optics
  • second harmonic generation
  • crystal structure
  • CRYSTAL-STRUCTURE
  • OPTICAL NONLINEARITY
  • SR
  • PB
  • BA
  • BR

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