Title: Investigation of Melting and Solidification of Thin Polycrystalline Silicon Films via Mixed-Phase Solidification
Description: Melting and solidification constitute the fundamental pathways through which a thin-film material is processed in many beam-induced crystallization methods. In this thesis, we investigate and leverage a specific beam-induced, melt-mediated crystallization approach, referred to as Mixed-Phase Solidification (MPS), to examine and scrutinize how a polycrystalline Si film undergoes the process of melting and solidification. On the one hand, we develop a more general understanding as to how such transformations can transpire in polycrystalline films. On the other hand, by investigating how the microstructure evolution is affected by the thermodynamic properties of the system, we experimentally reveal, by examining the solidified microstructure, fundamental information about such properties (i.e., the anisotropy in interfacial free energy). Specifically, the thesis consists of two primary parts: (1) conducting a thorough and extensive investigation of the MPS process itself, which includes a detailed characterization and analysis of the microstructure evolution of the film as it undergoes MPS cycles, along with additional development and refinement of a previously proposed thermodynamic model to describe the MPS melting-and-solidification process; and (2) performing MPS-based experiments that were systematically designed to reveal more information on the anisotropic nature of Si-SiO₂ interfacial energy (i.e., σ_{Si-SiO₂}).

MPS is a recently developed radiative-beam-based crystallization technique capable of generating Si films with a combination of several sought-after microstructural characteristics. It was conceived, developed, and characterized within our laser crystallization laboratory at Columbia University. A preliminary thermodynamic model was also previously proposed to describe the overall melting and solidification behavior of a polycrystalline Si film during an MPS cycle, wherein the grain-orientation-dependent solid-liquid interface velocity is identified as being the key parameter responsible for inducing the observed microstructure evolution. The present thesis builds on the abovementioned body of work on MPS. To this end, we note that the limited scope of previous investigations motivates us to perform more thorough characterization and analysis of the experimental results. Also, we endeavor to provide more involved explanations and expressions to account for the observed microstructure evolution in terms of the proposed thermodynamic model.

To accomplish these tasks forms the motivation for the first portion of this thesis. In this section we further develop the thermodynamic model by refining the expression for the solid-liquid interface velocities. In addition, we develop an expression for the grain-boundary-location-displacement distance in an MPS cycle. This is a key fundamental quantity that effectively captures the essence of the microstructure evolution resulting from MPS processing. Experimentally, we conduct a thorough investigation of the MPS process by focusing on examining the details of the microstructure evolution of {100}-surface-oriented grains. Firstly, we examine and analyze the gradual evolution in the microstructure of polycrystalline Si films being exposed to multiple MPS cycles. A Johnson-Mehl-Avrami-Kolmogorov-type (JMAK-type) analysis is proposed and developed to describe the microstructure transformation. Secondly, we investigate the behavior of grains with surface orientations close to the <100> pole.

Orientation-dependent (in terms of their extent of deviation from the <100> pole) microstructure evolution is revealed. This observation indicates that the microstructure of the film continues to evolve to form an even tighter distribution of grains around the <100> pole as the MPS process proceeds. During MPS melting-and-solidification cycles, a unique near-equilibrium environment is created and stabilized by radiative beam heating. Therefore, the microstructure of the resulting films is expected to be explicitly and dominantly affected by various thermodynamic properties of the system. Specifically, we identify the orientation-dependent value of the Si-SiO₂ interfacial energy as a key factor. This being the case, the MPS method actually provides us with an ideal platform to experimentally study the Si-SiO₂ interfacial energy. In the second part of this thesis, we perform MPS-based experiments to systematically investigate the orientation-dependent Si-SiO₂ interfacial energy. Two complementary approaches are designed and conducted, both of which are built on examining the texture evolution of different surface orientations resulting from MPS melting-and-solidification cycles.

The first approach, “Large-Area Statistical Analysis”, statistically examines the overall microstructure evolution of non-{100}-surface-oriented grains. By interpreting the changes in the surface-orientation distribution of the grains in terms of the thermodynamic model, we identify the orientation-dependent hierarchical order of Si-SiO₂ interfacial energies. The second approach, “Same-Area Local Analysis”, keeps track of the same set of grains that undergo several MPS cycles. An equivalent set of information on the Si-SiO₂ interfacial energy is extracted. Both methods reveal, in a consistent manner, an essentially identical Si-SiO₂ interfacial energy hierarchical order for a selected group of orientations. Also, the “Same-Area Local Analysis” provides some additional information that cannot otherwise be obtained (such as information about the evolution of two adjacent grains of specific orientations). Using such information and based on the grain-boundary-location-displacement distance derived using the thermodynamic model, we further deduce and evaluate the magnitude of Δσ_{Si-SiO₂} for certain orientation pairs.