Hydrogen elimination and phase transitions in pulsed-gas plasma deposition of amorphous and microcrystalline silicon

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Abstract
Removal of hydrogen from the growth surface during silane plasma deposition of silicon is correlated with the transition from amorphous to microcrystalline film structure. Plasma deposition experiments were performed using a pulsed gas technique, where repeated steps of thin amorphous silicon film deposition, and atomic hydrogen (or deuterium) exposure are used to form microcrystalline and polycrystalline thin films at substrate temperatures below 250 °C. Infrared absorption and Raman spectroscopy are used to estimate the silicon-hydrogen bonding concentrations, and characterize crystal structure, respectively. Hydrogen elimination probed using real-time differentially pumped mass spectroscopy demonstrates that during atomic deuterium exposure, hydrogen abstraction by deuterium, rather than silicon etching, is the primary mechanism for hydrogen removal from the depositing surface. Polycrystalline material, with no shoulder at 480 cm−1 in the Raman spectrum, and grain sizes greater than 1000 Å, as determined by transmission electron microscopy, have been formed at temperatures below 250 °C. The amorphous to crystal transition is observed at substrate temperatures as low as 25 °C, with longer hydrogen exposure required at lower temperatures. Hydrogen is shown to be preferentially abstracted from monohydride (Si–H) units as compared to dihydride (SiH2) units at or near the depositing growth surface, consistent with ab initio energy calculations of hydrogen interactions with silicon hydrides. A transition in hydrogen removal kinetics is observed upon film crystallization, where the rate of hydrogen removal is reduced for more crystalline materials. These results are valuable for understanding surface reactions in low temperature crystalline silicon deposition, for example, for fabrication of high mobility thin film transistor structures on glass.