Author

Wei Hong

Date of Graduation

2003

Document Type

Dissertation

Degree Type

PhD

College

Eberly College of Arts and Sciences

Department

Physics and Astronomy

Committee Chair

Larry E. Haliburton

Committee Co-Chair

Nancy C. Giles

Committee Member

Terry W. Gullion

Committee Member

Earl E. Scime

Committee Member

Mohindar S. Seehra

Abstract

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (EN-DOR) have been used to identify and characterize point defects in nonlinear optical crystals of lithium triborate (LiB3O5) and beta barium borate (β-BaB2O4). Two similar hole centers, one (Hole Center A) stable below approximately 130 K and the other one (Hole Center B) stable below approximately 170 K, were observed in LiB3O 5. For both centers, there is a major hyperfine interaction with only one 11B nucleus. The g matrix and the 11B hyperfine and nuclear quadrupole matrices have been determined for each hole center. I suggest Hole Center A is a self-trapped hole with the hole localized on an oxygen ion between a threefold-bonded boron and a fourfold-bonded boron. The self-trapping occurs because of a significant relaxation of the neighboring fourfold boron away from the hole. A similar model is suggested for Hole Center B, except a neighboring lithium vacancy is included to provide the increased thermal stability. For undoped β-BaB2O4, the dominant electron center is an oxygen vacancy on a bridging oxygen site. The EPR spectrum of this center exhibits a 16-line hyperfine pattern from two boron nuclei. The dominant hole center in β-BaB2O4 exhibits a four-line hyperfine pattern due to one boron, and is assigned to a hole localized on a nonbridging oxygen ion with no other defects nearby. Warming the crystal to approximately 80 K destroys the dominant hole spectrum and introduces other perturbed hole centers. For silver-doped β-BaB 2O4, after room temperature irradiation of the sample, EPR reveals a Ag2+ center (formed when a hole is trapped by a Ag + substituting on a Ba2+ site) and two distinct interstitial Ag0 centers (formed when an electron is trapped by a Ag + on interstitial sites). The g and A matrices of the Ag2+ center have been determined. These centers in LiB3O5 and β-BaB2O 4 are of interest because of their possible role in the unwanted transient optical absorption produced in these nonlinear optical crystals by high-power pulsed ultraviolet lasers.

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