In this paper, we show the coexistence of the bipolar and unipolar resistive-switching modes in NiO cells realized using an optimized oxidation process of a Ni blanket layer used as the bottom electrode. The two switching modes can be activated independent of the cell switching history provided the appropriate programming conditions are applied. The bipolar and unipolar switching modes are discussed as driven by electrochemical- and thermal-based mechanisms, respectively. The switching versatility between these two modes is demonstrated both for large oxidized Ni films and for Ni films oxidized at the bottom of small dimension contact holes. The perspective of selecting the desired switching mode in a scaled device made in a small diameter single hole is highly attractive because the specific advantages of the two modes broaden the application scope of the cell and enable larger flexibility in terms of memory architecture.

We demonstrate that electron trapping at intrinsic precursor sites is endemic in non-glass-forming amorphous oxide films. The energy distributions of trapped electron states in ultra-pure prototype amorphous (a)-HfO insulator obtained from exhaustive photo-depopulation experiments demonstrate electron states in the energy range of 2-3 eV below the oxide conduction band. These energy distributions are compared to the results of density functional calculations of a-HfO models of realistic density. The experimental results can be explained by the presence of intrinsic charge trapping sites formed by under-coordinated Hf cations and elongated Hf-O bonds in a-HfO. These charge trapping states can capture up to two electrons, forming polarons and bi-polarons. The corresponding trapping sites are different from the dangling-bond type defects responsible for trapping in glass-forming oxides, such as SiO, in that the traps are formed without bonds being broken. Furthermore, introduction of hydrogen causes formation of somewhat energetically deeper electron traps when a proton is immobilized next to the trapped electron bi-polaron. The proposed novel mechanism of intrinsic charge trapping in a-HfO represents a new paradigm for charge trapping in a broad class of non-glass-forming amorphous insulators.

Analysis of photodepopulation of electron traps in HfO2 films grown by atomic layer deposition is shown to provide the trap energy distribution across the entire oxide bandgap. The presence is revealed of two kinds of deep electron traps energetically distributed at around Et ≈ 2.0 eV and Et ≈ 3.0 eV below the oxide conduction band. Comparison of the trapped electron energy distributions in HfO2 layers prepared using different precursors or subjected to thermal treatment suggests that these centers are intrinsic in origin. However, the common assumption that these would implicate O vacancies cannot explain the charging behavior of HfO2, suggesting that alternative defect models should be considered.

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