Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Materials Science and Engineering


Ballato, John

Committee Member

Brown , Philip

Committee Member

Dong , Liang

Committee Member

Foulger , Stephen


Glass-clad optical fibers comprising a crystalline semiconductor core have garnered considerable recent attention for their potential utility as novel waveguides for applications in nonlinear optics, sensing, power delivery, and biomedicine.
As research into these fibers has progressed, it has become evident that excessive losses are limiting performance and so greater understanding of the underlying materials science, coupled with advances in fiber processing, is needed. More specifically, the semiconductor core fibers possess three performance-limiting characteristics that need to be addressed: (a) thermal expansion mismatches between crystalline core and glass cladding that lead to cracks, (b) the precipitation of oxide species in the core upon fiber cooling, which results from partial dissolution of the cladding glass by the core melt, and (c) polycrystallinity; all of which lead to scattering and increased transmission losses. This dissertation systematically studies each of these effects and develops both a fundamental scientific understanding of and practical engineering methods for reducing their impact.
With respect to the thermal expansion mismatch and, in part, the dissolution of oxides, for the first time to our knowledge, oxide and non-oxide glass compositions are developed for a series of semiconductor cores based on two main design criteria: (1) matching the thermal expansion coefficient between semiconductor core and glass cladding to minimize cracking and (2) matching the viscosity-temperature dependences, such that the cladding glass draws into fiber at a temperature slightly above the melting point of the semiconductor in order to minimize dissolution and improve the fiber draw process. The x[Na2O:Al2O3] + (100 - 2x)SiO2 glass compositional family was selected due to the ability to tailor the glass properties to match the aforementioned targets through slight variations in composition and adjusting the ratios of bridging and non-bridging oxygen; experimental results show a decrease in fiber core oxygen content in the fibers drawn with the tailored glass composition.
In a further attempt to reduce the presence of oxide species in the core, a reactive molten core approach to semiconductor optical fibers are developed. Specifically, the addition of silicon carbide (SiC) into a silicon (Si) core provides an in-situ reactive getter of oxygen during the draw process to achieve oxygen-free silicon optical fibers. Elemental analysis and x-ray diffraction of fibers drawn using this reactive chemistry approach show negligible oxygen concentration in the highly crystalline silicon core, a significant departure from the nearly 18 atom percent oxygen in previous fibers. Scattering of light out of the core is shown qualitatively to have been reduced in the process.
The role of the cross-sectional geometry on the resultant core crystallography with respect to the fiber axis is explored in a continued effort to better understand the nature of the crystal formation and structural properties in these semiconductor core optical fibers. A square cross-sectional geometry was explored to determine if core non-circularity can enhance or promote single crystallinity, as the semiconductors studied have a preference to form cubic crystals. Resultant crystallography of the non-circular core showed a significant improvement in maintaining a preferred crystallographic orientation, with the square core fibers exhibiting a 90% preference for the < 1 1 0 > family of directions occurring closest to the longitudinal direction of the fiber. The ability to orient the crystallography with respect to the fiber axis could be of great value to future nonlinear optical fiber-based devices.
In summary, this dissertation begins to elucidate some of the microstructural features, not present in conventional glass optical fibers, which could be important for future low-loss single crystalline semiconductor optical fibers. Additionally, this dissertation offers novel insight into the various aspects of materials science of non-conventional glass optical fibers, such as crystallization and solidification under highly non-equilibrium and confined conditions, phase equilibria and in-situ reactions, and the interplay between thermodynamics and kinetics.