Changes in the electronic structures of Ge2Sb2Te5 (GST) and N-doped Ge2Sb2Te5 film during the phase transition from an amorphous to a crystalline phase were studied using synchrotron radiation high-resolution x-ray photoemission spectroscopy. The changes in tetrahedral and octahedral coordinated Ge 3d peaks are closely related to the changes in the chemical bonding state of GST films. The metallic Sb peak in the Sb 4d spectra of annealed GST films demonstrates that the metallic Sb atoms become segregated during thermal treatment resulting in phase separation. The incorporation of nitrogen into the GST film affects its structure and chemical bonding state, resulting in the suppression of crystallization. The incorporation of nitrogen also increases the optical band gap of the film due to the formation of a nitride.
The effects of film composition and postnitridation annealing on band gap and valence band offset were examined in nitrided Hf-silicate films prepared using direct plasma nitridation. Regardless of the composition of Hf-silicate films, the band gap characteristics were similar after direct plasma nitridation (4.5±0.1eV) and postnitridation annealing (5.6±0.1eV). The decrease in band gap after direct plasma nitridation was caused by the formation of Si–N and Hf–N bonds, while the recovery of band gap by postnitridation annealing was influenced by the dissociation of unstable Hf–N bonds. The difference in valence band offset was strongly related to the chemical states of Si–N bonds.
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