Date of Award

8-2013

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Materials Science and Engineering

Advisor

Richardson, Kathleen

Committee Member

Luzinov , Igor

Committee Member

Foulger , Stephen

Committee Member

Ballato , John

Committee Member

Musgraves , David

Committee Member

Rodriguez , Vincent

Committee Member

Cardinal , Thierry

Committee Member

Richardson , Kathleen

Abstract

Tellurite-based oxide glasses have been investigated as promising materials for Raman gain applications, due to their good linear and nonlinear optical properties and their wide transparency windows in the near- and midwave infrared spectral region. Furthermore, their interesting thermal properties, i.e. low glass transition temperature and ability to be drawn into optical fibers, make tellurite-based glasses excellent candidates for optical fiber amplifiers. The estimation of the strength and spectral distribution of Raman gain in materials is commonly approximated from the spontaneous Raman scattering cross-section measurement. For development of tellurite-based glasses as Raman amplifiers, understanding the relationship between glass structure, vibrational response, and nonlinear optical properties (NLO) represents a key point. This dissertation provides an answer to the fundamental question of the Doctor of Philosophy (PhD) study: 'What is the impact of the glass structure on Raman gain properties of tellurite glasses?'
This dissertation summarizes findings on different tellurite-based glass families: the TeO2-TaO5/2-ZnO, TeO2-BiO3/2-ZnO and TeO2-NbO5/2 glass networks. The influence of glass modifiers has been shown on the glass' properties. Introduction of tantalum oxide or zinc oxide has been shown to increase the glass' stability against crystallization, quantified by T, where T = Tx-Tg. Added to the variation of the glass viscosity, this attribute is critical in fabricating optical fibers and for the use of these materials in fiber-based Raman gain applications. The role of ZnO in the tellurite network and the mechanism for structural modification has been determined. This addition results in not only the largest T reported for these highly nonlinear glasses to date, but coincides with a commensurate decrease of the refractive index. A hydroxyl purification has been developed that when employed, resulted in high purity preform materials exhibiting a limited absorption in the transmission bandwidth in the near infrared (NIR). A reduction of 90 % in the OH content in candidate glasses was realized and core-only optical fiber drawn from this glass exhibited optical losses lower than 10 dB/m (either at 1.55 μm or 2.0 μm). This optical attenuation in a high Raman gain material represents a first in the design of both material attributes.
The role of the glass modifiers on the glass structure has been investigated by a combination of vibrational spectroscopic methods, including IR absorption, as well as Raman and hyper-Raman scatterings. Following examination of fundamental vibrations present in the paratellurite crystal α-TeO2, these results were extended to interpret the structure of multi-component tellurite glasses. It has been verified that the transformation of the tellurite entities TeO4TeO3+1TeO3 is directly related to the percentage and type of glass modifiers present in the various tellurite glass matrix. The dramatic disruption in the continuity of Te-O linkages in the tellurite glass backbone's chains during the introduction of the modifier zinc oxide, leads to a systematic reduction in glass network connectivity. This structural change is accompanied by a significant change in the glass' normalized polarization curve ( ), a paramter which quantifies directly the depolymerization ratio (DR). This metric provides direct correlation with a reduction in the ternary glass' polarizability/hyperpolarizability and a decrease in the glass' nonlinear optical properties, specifically its Raman gain response. These results have validated and extended our understanding of the important role of Te-O-Te content and short, medium and longer-scale organization of the tellurite glass network and the corresponding impact on linear and nonlinear optical response and properties. Such fundamental knowledge of the relationship between vibrational response and structure, correlated to linear and nonlinear optical properties, allows the extension of this know-how to the development of customized optical components enabled by novel glass and glass ceramic optical materials.

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