Time-dependent electrostatic field-induced second-harmonic (TD-EFISH) generation is used to probe optically excited hot carrier injection (HCI) from silicon-on-insulator (SOI) films as thin as 2 nm into both native oxide and buried oxide (BOX), without device fabrication. The two HCI processes induce TD-EFISH signals of opposite sign, at different rates, whereby they are distinguished straightforwardly. HCI at the SOI/BOX interface is dominated by two-photon injection into HF defect induced traps created during SOI thinning. The results demonstrate that SHG can noninvasively and quantitatively characterize HCI, a key determinant of SOI device reliability.

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