Transient negative capacitance effects in epitaxial ferroelectric Pb(Zr₀.₂Ti₀.₈)O₃ capacitors are investigated with a focus on the dynamical switching behavior governed by domain nucleation and growth. Voltage pulses are applied to a series connection of the ferroelectric capacitor and a resistor to directly measure the ferroelectric negative capacitance during switching. A time-dependent Ginzburg-Landau approach is used to investigate the underlying domain dynamics. The transient negative capacitance is shown to originate from reverse domain nucleation and unrestricted domain growth. However, with the onset of domain coalescence, the capacitance becomes positive again. The persistence of the negative capacitance state is therefore limited by the speed of domain wall motion. By changing the applied electric field, capacitor area or external resistance, this domain wall velocity can be varied predictably over several orders of magnitude. Additionally, detailed insights into the intrinsic material properties of the ferroelectric are obtainable through these measurements. A new method for reliable extraction of the average negative capacitance of the ferroelectric is presented. Furthermore, a simple analytical model is developed, which accurately describes the negative capacitance transient time as a function of the material properties and the experimental boundary conditions.

The discovery of the ferroelectric orthorhombic phase in doped hafnia films has sparked immense research efforts. Presently, a major obstacle for hafnia's use in high-endurance memory applications like nonvolatile random-access memories is its unstable ferroelectric response during field cycling. Different mechanisms are proposed to explain this instability including field-induced phase change, electron trapping, and oxygen vacancy diffusion. However, none of these is able to fully explain the complete behavior and interdependencies of these phenomena. Up to now, no complete root cause for fatigue, wake-up, and imprint effects is presented. In this study, the first evidence for the presence of singly and doubly positively charged oxygen vacancies in hafnia–zirconia films using thermally stimulated currents and impedance spectroscopy is presented. Moreover, it is shown that interaction of these defects with electrons at the interfaces to the electrodes may cause the observed instability of the ferroelectric performance.

Ferroelektrische Materialien sind ein Schlüsselbereich der aktuellen Forschung und weisen zahlreiche wichtige technologische Anwendungen auf. Diese Klasse kristalliner Feststoffe zeichnet sich üblicherweise durch eine Vielzahl von para- und ferroelektrischen Phasen auf. Letztere sind dadurch charakterisiert, dass sie auch in Abwesenheit eines äußeren Feldes eine spontane elektrische Polarisation aufweisen. Diese Eigenschaft hat ihren Ursprung in der besonderen elektronischen Struktur ferroelektrischer Materialien, die sich aus einer großen Vielfalt von Gittergeometrien und mikroskopischen Ladungsdichteverteilungen ergibt. Auf atomarer Ebene sind die komplexen Eigenschaften der Ferroelektrika bis jetzt jedoch nur teilweise verstanden. Insbesondere die Verbindung zwischen mikroskopischen elektronischen Ladungsverteilungen und der daraus resultierenden makroskopischen elektrischen Polarisation wirft eine entscheidende, momentan noch offene Frage auf. Die Ladungsdynamik und ihr Zusammenspiel mit Gitteranregungen, insbesondere Softmoden, sind auf atomaren Längen- und Zeitskalen ungelöst. In dieser Arbeit wird das Potenzial der Femtosekunden-Röntgenpulverbeugung aufgezeigt, diese Frage zu adressieren. Diese Methode ermöglicht im Rahmen dieser Arbeit die Bestimmung transienter elektronischer Ladungsdichtekarten für das prototypische ferroelektrische Ammoniumsulfat direkt unterhalb seiner Curie-Temperatur nach einer optischen Anregung. Die Analyse der experimentellen Daten deckte eine bislang unbekannte niederfrequente Gitteroszillation mit einer Periode von 3 ps und nukleare Verschiebungen im Sub-Picometer-Bereich auf, die Ladungsverschiebungen auf einer 100-pm-Längenskala induzieren. Dies sind klare Merkmale, die auf die Anregung einer Softmode hinweisen. Schließlich wird zum ersten Mal die Dynamik der makroskopischen Polarisationsänderung abgeleitet, die eine oszillatorische Umkehr der Polarität aufweist und für ultraschnelle Schaltanwendungen geeignet ist. / Ferroelectrics are an area of current research, with important technological applications such as ferroelectric random access memories, infrared cameras or medical ultrasound equipment. This class of crystalline solids do not commonly only exhibit a ferroelectric phase, but rather go through an abundant variety of para- and ferroelectric phases that depend on the temperature. The ferroelectric phases present a spontaneous electric polarization even in the absence of an external field, in contrast to paraelectric phases and also exhibit a hysteresis loop in analogy to ferromagnets. This macroscopic feature has its origin in their peculiar electronic structure, which results from a rich diversity of lattice geometries and complex microscopic charge distributions. At the atomic level, however, the intricate characteristics of ferroelectrics are only partially understood. The link between microscopic charge distributions and macroscopic electric polarization poses a crucial question to be solved. The interplay of charge dynamics and lattice excitations are still unresolved on atomic length and time scales. In this thesis, femtosecond X-Ray powder diffraction is used to find solutions for these unanswered questions. This method allows for the experimental determination of time-resolved charge density maps from where the structural, charge and polarization dynamics are can be derived. These maps are determined for the photoexcited ferroelectric ammonium sulphate just below its Curie temperature. Data analysis has revealed a newly discovered low frequency lattice oscillation with a 3ps period and sub-picometer nuclear displacements that is related to periodic charge relocations on a 100pm length scale, which is a feature indicative of soft mode behavior. Finally, the dynamics of the variation of polarization are derived for the first time, showing an oscillatory reversal of polarity that holds potential for ultrafast switching applications.

The properties of ferroelectric materials, which were discovered almost a century ago¹ , have led to a huge range of applications, such as digital information storage² , pyroelectric energy conversion³ and neuromorphic computing⁴⁻⁵ . Recently, it was shown that ferroelectrics can have negative capacitance⁶⁻¹¹, which could improve the energy efficiency of conventional electronics beyond fundamental limits¹²⁻¹⁴. In Landau–Ginzburg–Devonshire theory¹⁵⁻¹⁷, this negative capacitance is directly related to the doublewell shape of the ferroelectric polarization–energy landscape, which was thought for more than 70 years to be inaccessible to experiments¹⁸. Here we report electrical measurements of the intrinsic double-well energy landscape in a thin layer of ferroelectric Hf₀.₅Zr₀.₅O₂. To achieve this, we integrated the ferroelectric into a heterostructure capacitor with a second dielectric layer to prevent immediate screening of polarization charges during switching. These results show that negative capacitance has its origin in the energy barrier in a double-well landscape. Furthermore, we demonstrate that ferroelectric negative capacitance can be fast and hysteresis-free, which is important for prospective applications¹⁹. In addition, the Hf₀.₅Zr₀.₅O₂ used in this work is currently the most industry-relevant ferroelectric material, because both HfO₂ and ZrO₂ thin films are already used in everyday electronics²⁰. This could lead to fast adoption of negative capacitance effects in future products with markedly improved energy efficiency.

No description available.

No description available.

The discovery of ferroelectricity in hafnium oxide has revived the interest in ferroelectric memories as a viable option for low power non-volatile memories. However, due to the high coercive field of ferroelectric hafnium oxide, instabilities in the field cycling process are commonly observed and explained by the defect movement, defect generation and field induced phase transitions. In this work, the optical and transport experiments are combined with ab-initio simulations and transport modeling to validate that the defects which act as charge traps in ferroelectric active layers are oxygen vacancies. A new oxygen vacancy generation leads to a fast growth of leakage currents and a consequent degradation of the ferroelectric response in Hf₀.₅Zr₀.₅O₂ films. Two possible pathways of the Hf₀.₅Zr₀.₅O₂ ferroelectric property degradation are discussed.

The Rayleigh law describes the linear dependence of the permittivity of a ferroelectric on the applied ac electric field amplitude due to irreversible motions of domain walls. We show that this gives rise to a new equivalent-circuit element predestined to fit the impedance spectra of ferroelectrics based on an accepted physical model. Such impedance spectroscopy is a powerful tool to obtain a dielectric and resistive representation of the entire sample structure. The superiority of the Rayleigh analysis based on impedance spectroscopy compared to the common single-frequency approach is demonstrated for a ferroelectric Si : HfO₂ thin film

With the discovery of the ferroelectric (FE) properties within HfO₂, the scaling gap between state-of-the-art technology nodes and non-volatile memories based on FE materials can be bridged. In addition to non-volatility, new memory concepts should guarantee sufficient endurance and operation stability. However, in contrast to optimized perovskite based FEs, binary oxide based FE memories still show changes in the memory window (MW) followed by either hard breakdown or closure of the MW. Recently, we have shown that anti-FE (AFE) materials exhibit very stable and significantly higher endurance with respect to the FE counterparts. Inspired by the robustness and remarkable cycling performance of the AFE materials, we analyze the remaining reliability aspects of these devices. By characterizing the pure film properties of capacitor stacks and switching performance when integrated into devices, we compare and investigate temperature stability, imprint, retention, and variability of both FE and AFE memories. We investigate if the lower energetic barrier to be overcome together with partial switching and lower switching induced stress are responsible for the higher endurance of the AFE with respect to the FE based memories. By utilizing charge trapping and charge pumping tests together with leakage current spectroscopy in combination with comprehensive modeling we check that assumption. Moreover, we identify the interfacial buffer layer as the weakest link of these devices.

This letter investigates the impact of self-heating on the post-cycling functionality of a scaled hafnium oxide-based ferroelectric field-effect transistor (FeFET). The full recovery of FeFET switching properties and data retention after the cycling endurance failure is reported. This is achieved by damage annealing through localized heating, which is intentionally induced by a large current flow through the drain (source)-body p-n junctions. The results highlight that the local thermal treatments could be exploited to extend the cycling endurance of FeFETs.