Chemical vapor deposition of boron carbo-nitride as a potential passivation layer for germanium surfaces
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Motivated by the need for a Ge surface passivation layer, chemical vapor deposition of thin (< 10 nm) films of amorphous boron carbo-nitride (BCxNy) on Ge(100) surfaces were studied to assess film continuity, interface bonding, Ge oxidation prevention, and electrical passivation. BCxNy nominally 2.5-5 nm thick continuously covers Ge(100), as determined by ion scattering spectroscopy and two angle resolved x-ray photoelectron spectroscopy (ARXPS) techniques. ARXPS analysis reveals no evidence of an interfacial layer due to elemental intermixing at the BCxNy-Ge(100) interface. High resolution transmission electron microscopy images of HfO₂ / BCxNy / Ge(100) cross-sections reveal abrupt BCxNy-Ge(100) interfaces. XPS was used to track Ge oxidation of BCxNy-covered Ge(100) upon exposure to ambient, 50 °C deionized water, and a 250 °C atomic layer deposition HfO₂ process. If the BCxNy layer is continuous ([greater-than or equal to] ~ 4 nm), the underlying Ge(100) surface is not oxidized despite incorporation of O into BCxNy. Thinner films ([less than or equal to] 3.2 nm) permitted Ge(100) oxidation in each oxidizing environment studied. Ge nanowires with a 5.7 nm BCxNy coating were resistant to oxidation for at least 5 months of ambient exposure. C-V and I-V measurements were made for metal-insulator-semiconductor (MIS) structures fabricated from n-Si(100) and n-Ge(100) wafers passivated with 4.5-5 nm BCxNy. C-rich BC0.61N0.08 films studied up to this point exhibited large amounts of hysteresis and fixed negative charge, so they were abandoned in favor of N-rich BCxNy (0.09 [less than or equal to] x [less than or equal to] 0.15, 0.38 [less than or equal to] y [less than or equal to] 0.52). N-rich BCxNy grown at 275-400 °C showed that lower deposition temperatures resulted in improved electrical characteristics, including decreased hysteresis, lower VFB shift, lower leakage current, and less C-V stretch-out. The electrical improvement is attributed to decreased bulk and interfacial defects in BCxNy deposited at lower temperatures. Even for the lowest growth temperature studied (275 °C), BCxNy-passivated Ge(100) devices had considerable hysteresis and electrical characteristics worsened after a post-metallization anneal. BCxNy-passivated Si(100) devices outperformed similar Ge(100) devices, likely due to the higher interface state densities at the BCxNy-Ge(100) interface associated with the higher relative inertness of Ge(100) to thermal nitridation.