Mechanical Properties of Photovoltaic Silicon in Relation to Wafer Breakage.

摘要

This thesis focuses on the fundamental understanding of stress-modified crack-propagation in photovoltaic (PV) silicon in relation to the critical issue of PV silicon "wafer breakage". The interactions between a propagating crack and impurities/defects/residual stresses have been evaluated for consequential fracture path in a thin PV Si wafer. To investigate the mechanism of brittle fracture in silicon, the phase transformations induced by elastic energy released at a propagating crack-tip have been evaluated by locally stressing the diamond cubic Si lattice using a rigid Berkovich nanoindenter tip (radius ≈50 nm). Unique pressure induced phase transformations and hardness variations have been then related to the distribution of precipitates (O, Cu, Fe etc.), and the local stresses in the wafer.;This research demonstrates for the first time the "ductile-like fracture" in almost circular crack path that significantly deviates from its energetically favorable crystallographic [110](111) system. These large diameter (≈ 200 mm) Si wafers were sliced to less than 180 µm thickness from a Czochralski (CZ) ingot that was grown at faster than normal growth rates. The vacancy (vSi) driven precipitation of oxygen at enhanced thermal gradients in the wafer core develops large localized stresses (upto 100 MPa) which we evaluated using Raman spectral analysis. Additional micro-FTIR mapping and microscopic etch pit measurements in the wafer core have related the observed crack path deviations to the presence of concentric ring-like distributions of oxygen precipitates (OPs).;To replicate these "real-world" breakage scenarios and provide better insight on crack-propagation, several new and innovative tools/devices/methods have been developed in this study. An accurate quantitative profiling of local stress, phase changes and load-carrying ability of Si lattice has been performed in the vicinity of the controlled micro-cracks created using micro-indentations to represent the surface/edge micro-cracks (i.e. sources of crack initiation). The low load (<10mN) nanoindentations using Hysitron Triboindenter ® have been applied to estimate the zone of crack-propagation related plastic deformation and amorphization around the radial or the lateral cracks. The gradual reduction in hardness due to local stress field and phase change around the crack has been established using electron back scattered diffraction (EBSD), atomic force microscopy (AFM) and Raman spectroscopy, respectively, at nano- and micro-scale. The load (P) vs. displacement (h) curves depict characteristic phase transformation events (eg. elbow or pop-out) depending on the sign of residual stress in the silicon lattice. The formation of Si-XII/III phases (elastic phases) in large volumes during indentation of compressed Si lattice have been discussed as an option to eliminate the edge micro-cracks formed during wafer sawing by ductile flow.;The stress gradient at an interface, which can be a grain-boundary (GB), twin or a interface between silicon and precipitate, has been evaluated for crack path modification. An direct-silicon-bonded (DSB) based ideal [110]/[100] interface has been examined to study the effect of crystallographic orientation variation across a planar silicon 2D boundary. Using constant source diffusion/annealing process, Fe and Cu impurities have been incorporated in model [110]/[100]GB to provide equivalence to a real decorated multi-crystalline grain boundary. We found that Fe precipitates harden the undecorated GB structure, whereas Cu precipitates introduce dislocation-induced plasticity to soften it. Aluminum Schottky diodes have been evaporated on the DSB samples to sensitively detect the instantaneous current response from the phase-transformed Si under nanoindenter tip. The impact of metallic impurity and their precipitates on characteristic phase transformations (i.e. pop-in or pop-out) demonstrate that scattered distribution of large Cu-precipitates (upto 50 nm) compresses Si-lattice to facilitate Si-XII/III formations, i.e. high pressure ductile phases. Sweeping voltage measurements at a given load determine that Si lattice has to be stressed beyond 1 mN to complete the Si-I (semiconducting) to Si-II (ohmic) phase changes. Above 1 mN load DSB sample has a varistor-like behavior due to higher grain-boundary resistance from interfacial states.;The precipitate defect structure stimulated stresses at the bulk Si lattice or grain boundary modify the rate of elastic energy release at the crack-tip and associated phase change and hardness values in response to external loading. The systematic approach in this thesis elucidates that the interfacial surface area between Si-lattice and precipitate plays pivotal role in defining extent of stresses in the silicon, i.e. smaller precipitates in higher densities are severe than few larger volume precipitates. The finding of high-pressure ductile phase formation during loading of compressed silicon structure has been suggested to PV industry as a prospective candidate for reducing the wafer breakage and allowing larger handling stresses.