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HfO2-based dielectrics are promising for nanoscale ferroelectric applications, and the most favorable material within the family is Zr-substituted hafnia, i.e., Hf1−xZrxO2 (HZO). The extent of Zr substitution can be great, and x is commonly set to 0.5. However, the bandgap of ZrO2 is lower than HfO2, thus it is uncertain how the Zr content should influence the electronic band structure of HZO. A reduced bandgap is detrimental to the cycling endurance as charge injection and dielectric breakdown would become easier. Another issue is regarding the comparison on the bandgaps between HfO2/ZrO2 superlattices and HZO solid-state solutions. In this work, we systematically investigated the electronic structures of HfO2, ZrO2, and HZO using self-energy corrected density functional theory. In particular, the conduction band minimum of Pca21-HfO2 is found to lie at an ordinary k-point on the Brillouin zone border, not related to any interlines between high-symmetry k-points. Moreover, the rule of HZO bandgap variation with respect to x has been extracted. The physical mechanisms for the exponential reduction regime and linear decay regime have been revealed. The bandgaps of HfO2/ZrO2 ferroelectric superlattices are investigated in a systematic manner, and the reason why the superlattice could possess a bandgap lower than that of ZrO2 is revealed through comprehensive analysis. [ABSTRACT FROM AUTHOR]

Conductive bridge random access memories (CBRAMs) usually involve active Ag or Cu metals, where the formation of metal filaments accounts for the low resistance state. For the application of neuromorphic computation, it is highly desirable to develop artificial neurons and synapses, which utilize the complicated volatile or nonvolatile resistive switching phenomena, respectively. This can be achieved by controlling the morphology and stability of the filaments, which requires a deep understanding of the filament formation and disruption mechanisms. Using ab initio calculations, we explored the physical mechanism behind various Ag filament morphologies and growth modes, using GeSe, ZrO2, SiO2, and a-Si as the examples. The roles of Ag and Ag+ stability inside the dielectric, the migration barrier of Ag+, and the Ag+ solvation effect have been investigated in detail. A comprehensive model has been proposed, which in particular could explain the diverse Ag filament morphology experimentally observed in sputtered SiO2 and PECVD SiO2. Our theoretical approach can serve as a pre-screening method in designing new solid-state electrolyte materials of CBRAM, aiming at new functionalities in neuromorphic computation or in-memory logic computing. [ABSTRACT FROM AUTHOR]

Ultra-thin ferroelectric hafnia-based thin films are very promising candidates for nanoscale ferroelectric random access memories. However, dielectric breakdown is a main failure mechanism during repeated polarization switching. Generalizing Lou et al.'s local phase decomposition model, originally for ferroelectric fatigue, we propose a dielectric breakdown model for ferroelectric hafnia. While charging injection during the polarization reversal is regarded as a key step, eventual phase separation of the Hf cluster accounts for the dielectric breakdown. Using this model, we explain why TaN/HfO2/TaN ferroelectric capacitors are more prone to dielectric breakdown than TiN/HfO2/TiN, and conclude that the lower Schottky barrier for the TaN/Pca21-HfO2 interface stabilizes neutral oxygen vacancies within the dielectric. On the other hand, when TiN electrodes are employed, oxygen vacancies tend to be positively charged. They can further pin the domain walls, resulting in ferroelectric fatigue. The relationship between the conductive filament formation, dielectric breakdown, wake up, and fatigue in ferroelectric HfO2 is discussed within the framework of our model. [ABSTRACT FROM AUTHOR]

The stability and aggregation mechanisms of oxygen vacancy chains are studied for hafnia using self-energy corrected density functional theory. While oxygen vacancies tend not to align along the c-axis of monoclinic HfO2, oxygen vacancy chains along a-axis and b-axis are energetically favorable, with cohesive energies of 0.05 eV and 0.03 eV per vacancy, respectively. Nevertheless, with an increase of the cross section area, intensive oxygen vacancy chains become much more stable in hafnia, which yields phase separation into Hf-clusters and HfO2. Compared with disperse single vacancy chains, intensive oxygen vacancy chains made of 4, 6, and 8 single vacancy chains are energetically more favorable by 0.17, 0.20, and 0.30 eV per oxygen vacancy, respectively. On the other hand, while a single oxygen vacancy chain exhibits a tiny electronic energy gap of around 0.5 eV, metallic conduction emerges for the intensive vacancy chain made of 8 single vacancy chains, which possesses a filament cross section area of ∼0.4 nm2. This sets a lower area limit for Hf-cluster filaments from metallic conduction point of view, but in real hafnia resistive RAM devices the cross section area of the filaments can generally be much larger (>5 nm2) for the sake of energy minimization. Our work sets up a bridge between oxygen vacancy ordering and phase separation in hafnia, and shows a clear trend of filament stabilization with larger dimensions. The results could explain the threshold switching phenomenon in hafnia when a small AFM tip was used as the top electrode, as well as the undesired multimode operation in resistive RAM cells with 3 nm-thick hafnia. [ABSTRACT FROM AUTHOR]

The crystal orientations and electrical properties of Bi4Ti3O12 (BIT) and Bi3.25La0.75Ti3O12 (BLT) ferroelectric thin films were studied and compared. Stoichiometric BIT and BLT samples were deposited on Pt(111) substrates and crystallized at 750 °C to get mixed orientations. The BIT sample exhibited a/b axes orientation with (117) component, while the BLT sample was more c-axis oriented. The 2Pr values of such BIT and BLT were 34.3 μC/cm2 and 25.7 μC/cm2, respectively. Nevertheless, BLT has much better leakage current and polarization saturation properties. In order to obtain c-axis oriented BIT thin films, excess bismuth was used. BIT with 15% excess bismuth processed at 750 °C was purely c-axis oriented and only possessed a 2Pr value of 4.9 μC/cm2, while that of 15% excess bismuth BLT sample was 18.3 μC/cm2. This can be attributed to the large polarization anisotropy in BIT, and this anisotropy is reduced by lanthanum doping. [ABSTRACT FROM AUTHOR]