Ferroelectricity is a material property were a remanent polarization exists under zero electrical field that can be reversed by applying an electrical field [1]. As consequence, two nonvolatile states exist that can be switched by an electrical field. This feature makes ferroelectrics ideally suited for nonvolatile memories with low write energy. Therefore, already in the 1950s first attempts have been made to realize ferroelectric nonvolatile memories based on ferroelectric barium titanate (BTO) crystals having evaporated electrodes on both sides [2]. The success of this approach was hindered by disturb issues that could be solved in the early 1990s by adding a transistor device as a selector [3]. Such a memory is referred to as a ferroelectric random access memory (FeRAM). Since reading of the ferroelectric polarization from a capacitor requires switching of the ferroelectric [1], the information will be destroyed and a write back is necessary. This can be avoided if the ferroelectric is placed inside of the gate stack of a MOS transistor resulting in a ferroelectric field effect transistor (FeFET) [1]. Conventional ferroelectric materials like BTO or lead- zirconium titanate (PZT) cannot be placed directly on silicon since unwanted interface reactions will occur. The necessary interface layer together with the space charge region of the transistor device leads to a rather low capacitance in series with the ferroelectric dielectric and consequently results in a strong depolarization field that has destroyed the nonvolatility of the FeFET device for many years and hinters scaling as well [4]. Today FeRAM devices are established on the market [3,5], but are limited to niche application since scaling is hindered by many integration problems associated to materials like PZT.

Visualization of domain structure evolution under an electrical bias has been carried out in ferroelectric La:HfO2 capacitors by a combination of Piezoresponse Force Microscopy (PFM) and pulse switching techniques to study the nanoscopic mechanism of polarization reversal and the wake-up process. It has been directly shown that the main mechanism behind the transformation of the polarization hysteretic behavior and an increase in the remanent polarization value upon the alternating current cycling is electrically induced domain de-pinning. PFM imaging and local spectroscopy revealed asymmetric switching in the La:HfO2 capacitors due to a significant imprint likely caused by the different boundary conditions at the top and bottom interfaces. Domain switching kinetics can be well-described by the nucleation limited switching model characterized by a broad distribution of the local switching times. It has been found that the domain velocity varies significantly throughout the switching process indicating strong interaction with structural defects.

The change of the spontaneous polarization due to a change of temperature is known as the pyroelectric effect and is restricted to crystalline, non-centrosymmetric and polar matter. Its main application is the utilization in infrared radiation sensors, but usage for waste heat energy harvesting or chemical catalysis is also possible. A precise quantification, i.e. the measurement of the pyroelectric coefficient p, is inevitable to assess the performance of a material. Hence, a comprehensive overview is provided in this work, which summarizes and evaluates the available techniques to characterize p. A setup allowing the fully automated measurement of p by utilizing the Sharp-Garn method and the measurement of ferroelectric hysteresis loops is described. It was used to characterize and discuss the behavior of p with respect to the temperature of the doped bulk III-V compound semiconductors gallium nitride and aluminum nitride and thin films of doped hafnium oxide, as reliable data for these materials is still missing in the literature. Here, the nitride-based semiconductors show a comparable small p and temperature dependency, which is only slightly affected by the incorporated dopant, compared to traditional ferroelectric oxides. In contrast, p of HfO2 thin films is about an order of magnitude larger and seems to be affected by the present dopant and its concentrations, as it is considered to be responsible for the formation of the polar orthorhombic phase.:1. Motivation and Introduction 2. Fundamentals 2.1. Dielectrics and their Classification 2.2. Polarization 2.3. Pyroelectricity 2.4. Ferroelectricty 2.5. Phase Transitions 2.6. Applications and Figures of Merit 3. Measurement Methods for the Pyroelectric Coefficient 3.1. General Considerations 3.1.1. Heating Concepts 3.1.2. Thermal Equilibrium 3.1.3. Electric Contact 3.1.4. Separation of Contributions 3.1.5. Thermally Stimulated Currents 3.2. Static Methods 3.2.1. Charge Compensation Method 3.2.2. Hysteresis Measurement Method 3.2.3. Direct Electrocaloric Measurement 3.2.4. Flatband Voltage Shift 3.2.5. X-ray Photoelectron Spectroscopy Method 3.2.6. X-ray Diffraction and Density Functional Theory 3.3. Dynamic Methods 3.3.1. Temperature Ramping Methods 3.3.2. Optical Methods 3.3.3. Periodic Pulse Technique 3.3.4. Laser Intensity Modulation Methods 3.3.5. Harmonic Waveform Techniques 4. Pyroelectric and Ferroelectric Characterization Setup 4.1. Pyroelectric Measurement Setup 4.1.1. Setup and Instrumentation 4.1.2. Automated Sharp-Garn Evaluation of Pyroelectric Coefficients 4.1.3. Further Examples 4.2. Hysteresis Loop Measurements 4.2.1. Instrumentation 4.2.2. Measurement and Evaluation 4.2.3. Examples 5. Investigated Material Systems 5.1. III-Nitride Bulk Semiconductors GaN and AlN 5.1.1. General Structure and Spontaneous Polarization 5.1.2. Applications 5.1.3. Crystal Growth and Doping 5.1.4. Pyroelectricity 5.2. Hafnium Oxide Thin Films 5.2.1. General Structure and Applications 5.2.2. Polar Properties in Thin Films 5.2.3. Doping Effects 5.2.4. Pyro- and Piezoelectricity 6. Results 6.1. The Pyroelectric Coefficient of Free-standing GaN and AlN 6.1.1. Sample Preparation 6.1.2. Pyroelectric Measurements 6.1.3. Lattice Influence 6.1.4. Slope Differences 6.2. Pyroelectricity of Doped Hafnium Oxide 6.2.1. Sharp-Garn Measurement on Thin Films 6.2.2. Effects of Silicon Doping 6.2.3. Dopant Comparison 7. Summary and Outlook A. Pyroelectric Current and Phase under Periodic Thermal Excitation B. Loss Current Correction for Shunt Method C. Conductivity Correction D. Comparison of Pyroelectric Figures of Merit Bibliography Publication List Acknowledgments / Die Änderung der spontanen Polarisation durch eine Änderung der Temperatur ist bekannt als der pyroelektrische Effekt, welcher auf kristalline, nicht-zentrosymmetrische und polare Materie beschränkt ist. Er findet vor allem Anwendung in Infrarot-Strahlungsdetektoren, bietet aber weitere Anwendungsfelder wie die Niedertemperatur-Abwärmenutzung oder die chemische Katalyse. Eine präzise Quantifizierung, d. h. die Messung des pyroelektrischen Koeffizienten p, ist unabdingbar, um die Leistungsfähigkeit eines Materials zu bewerten. Daher bietet diese Arbeit u.a. einen umfassenden Überblick und eine Bewertung der verfügbaren Messmethoden zur Charakterisierung von p. Weiterhin wird ein Messaufbau beschrieben, welcher die voll automatisierte Messung von p mit Hilfe der Sharp-Garn Methode und auch die Charakterisierung der ferroelektrischen Hystereseschleife ermöglicht. Aufgrund fehlerender Literaturdaten wurde dieser Aufbau anschließend genutzt, um den temperaturabhängigen pyroelektrischen Koeffizienten der dotierten III-V-Verbindungshalbleiter Gallium- und Aluminiumnitrid sowie dünner Schichten bestehend aus dotiertem Hafniumoxid zu messen und zu diskutieren. Im Vergleich zu klassichen ferroelektrischen Oxiden zeigen dabei die nitridbasierten Halbleiter einen geringen pyroelektrischen Koeffizienten und eine kleine Temperaturabhängigkeit, welche auch nur leicht durch den vorhandenen Dotanden beeinflusst werden kann. Dagegen zeigen dünne Hafniumoxidschichten einen um eine Größenordnung größeren pyroelektrischen Koeffizienten, welcher durch den anwesenden Dotanden und seine Konzentration beeinflusst wird, da dieser verantwortlich für die Ausbildung der polaren, orthorhombischen Phase gemacht wird.:1. Motivation and Introduction 2. Fundamentals 2.1. Dielectrics and their Classification 2.2. Polarization 2.3. Pyroelectricity 2.4. Ferroelectricty 2.5. Phase Transitions 2.6. Applications and Figures of Merit 3. Measurement Methods for the Pyroelectric Coefficient 3.1. General Considerations 3.1.1. Heating Concepts 3.1.2. Thermal Equilibrium 3.1.3. Electric Contact 3.1.4. Separation of Contributions 3.1.5. Thermally Stimulated Currents 3.2. Static Methods 3.2.1. Charge Compensation Method 3.2.2. Hysteresis Measurement Method 3.2.3. Direct Electrocaloric Measurement 3.2.4. Flatband Voltage Shift 3.2.5. X-ray Photoelectron Spectroscopy Method 3.2.6. X-ray Diffraction and Density Functional Theory 3.3. Dynamic Methods 3.3.1. Temperature Ramping Methods 3.3.2. Optical Methods 3.3.3. Periodic Pulse Technique 3.3.4. Laser Intensity Modulation Methods 3.3.5. Harmonic Waveform Techniques 4. Pyroelectric and Ferroelectric Characterization Setup 4.1. Pyroelectric Measurement Setup 4.1.1. Setup and Instrumentation 4.1.2. Automated Sharp-Garn Evaluation of Pyroelectric Coefficients 4.1.3. Further Examples 4.2. Hysteresis Loop Measurements 4.2.1. Instrumentation 4.2.2. Measurement and Evaluation 4.2.3. Examples 5. Investigated Material Systems 5.1. III-Nitride Bulk Semiconductors GaN and AlN 5.1.1. General Structure and Spontaneous Polarization 5.1.2. Applications 5.1.3. Crystal Growth and Doping 5.1.4. Pyroelectricity 5.2. Hafnium Oxide Thin Films 5.2.1. General Structure and Applications 5.2.2. Polar Properties in Thin Films 5.2.3. Doping Effects 5.2.4. Pyro- and Piezoelectricity 6. Results 6.1. The Pyroelectric Coefficient of Free-standing GaN and AlN 6.1.1. Sample Preparation 6.1.2. Pyroelectric Measurements 6.1.3. Lattice Influence 6.1.4. Slope Differences 6.2. Pyroelectricity of Doped Hafnium Oxide 6.2.1. Sharp-Garn Measurement on Thin Films 6.2.2. Effects of Silicon Doping 6.2.3. Dopant Comparison 7. Summary and Outlook A. Pyroelectric Current and Phase under Periodic Thermal Excitation B. Loss Current Correction for Shunt Method C. Conductivity Correction D. Comparison of Pyroelectric Figures of Merit Bibliography Publication List Acknowledgments

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In an era in which the amount of produced and stored data continues to exponentially grow, standard memory concepts start showing size, power consumption and costs limitation which make the search for alternative device concepts essential. Within a context where new technologies such as DRAM, magnetic RAM, resistive RAM, phase change memories and eFlash are explored and optimized, ferroelectric memory devices like FeRAM seem to showcase a whole range of properties which could satisfy market needs, offering the possibility of creating a non-volatile RAM. In fact, hafnia and zirconia-based ferroelectric materials opened up a new scenario in the memory technology scene, overcoming the dimension scaling limitations and the integration difficulties presented by their predecessors perovskite ferroelectrics. In particular, HfₓZr₁₋ₓO₂ stands out because of high processing flexibility and ease of integration in the standard semiconductor industry process flows for CMOS fabrication. Nonetheless, further understanding is necessary in order tocorrelate device performance and reliability to the establishment of ferroelectricity itself. The aim of this work is to investigate how the composition of the ferroelectric oxide, together with the one of the electrode materials influence the behavior of a ferroelectric RAM. With this goal, different process parameters and reliability properties are considered and an analysis of the polarization reversal is performed. Starting from undoped hafnia and zirconia and subsequently examining their intermixed system, it is shown how surface/volume energy contributions, mechanical stress and oxygen-related defects all concur in the formation of the ferroelectric phase. Based on the process optimization of an HfₓZr₁₋ₓO₂-based capacitor performed within these pages, a 64 kbit 1T1C FeRAM array is demonstrated by Sony Semiconductor Solutions Corporation which shows write voltage and latency as low as 2.0 V and 16 ns, respectively. Outstanding retention and endurance performances are also predicted, which make the addressed device an extremely strong competitor in the semiconductor scene.

The electric-field-driven and reversible polarization switching in ferroelectric materials provides a promising approach for nonvolatile information storage. With the advent of ferroelectricity in hafnium oxide, it has become possible to fabricate ultrathin ferroelectric films suitable for nanoscale electronic devices. Among them, ferroelectric field-effect transistors (FeFETs) emerge as attractive memory elements. While the binary switching between the two logic states, accomplished through a single voltage pulse, is mainly being investigated in FeFETs, additional and unusual switching mechanisms remain largely unexplored. In this work, we report the natural property of ferroelectric hafnium oxide, embedded within a nanoscale FeFET, to accumulate electrical excitation, followed by a sudden and complete switching. The accumulation is attributed to the progressive polarization reversal through localized ferroelectric nucleation. The electrical experiments reveal a strong field and time dependence of the phenomenon. These results not only offer novel insights that could prove critical for memory applications but also might inspire to exploit FeFETs for unconventional computing.

Ferroelectrics are promising for nonvolatile memories. However, the difficulty of fabricating ferroelectric layers and integrating them into complementary metal oxide semiconductor (CMOS) devices has hindered rapid scaling. Hafnium oxide is a standard material available in CMOS processes. Ferroelectricity in Si-doped hafnia was first reported in 2011, and this has revived interest in using ferroelectric memories for various applications. Ferroelectric hafnia with matured atomic layer deposition techniques is compatible with three-dimensional capacitors and can solve the scaling limitations in 1-transistor-1-capacitor (1T-1C) ferroelectric random-access memories (FeRAMs). For ferroelectric field-effect-transistors (FeFETs), the low permittivity and high coercive field Ec of hafnia ferroelectrics are beneficial. The much higher Ec of ferroelectric hafnia, however, makes high endurance a challenge. This article summarizes the current status of ferroelectricity in hafnia and explains how major issues of 1T-1C FeRAMs and FeFETs can be solved using this material system.

The new class of fully silicon-compatible hafnia-based ferroelectrics with high switchable polarization and good endurance and thickness scalability shows a strong promise for new generations of logic and memory devices. Among other factors, their competitiveness depends on the power efficiency that requires reliable low-voltage operation. Here, we show genuine ferroelectric switching in HfₓZr₍₁₋ₓ₎ O₂ (HZO) layers in the application-relevant capacitor geometry, for driving signals as low as 800 mV and coercive voltage below 500 mV. Enhanced piezoresponse force microscopy with sub-picometer sensitivity allowed for probing individual polarization domains under the top electrode and performing a detailed analysis of hysteretic switching. The authentic local piezoelectric loops and domain wall movement under bias attest to the true ferroelectric nature of the detected nanodomains. The systematic analysis of local piezoresponse loop arrays reveals a totally unexpected thickness dependence of the coercive fields in HZO capacitors. The thickness decrease from 10 to 7 nm is associated with a remarkably strong decrease of the coercive field, with about 50% of the capacitor area switched at coercive voltages ≤0.5 V. Our explanation consistent with the experimental data involves a change of mechanism of nuclei-assisted switching when the thickness decreases below 10 nm. The practical implication of this effect is a robust ferroelectric switching under the millivolt-range driving signal, which is not expected for the standard coercive voltage scaling law. These results demonstrate a strong potential for further aggressive thickness reduction of HZO layers for low-power electronics.

Hafnium oxide (HfO₂)-based ferroelectric field-effect transistor (FeFET) is an attractive device for nonvolatile memory. However, when compared to the well-established flash devices, the memory window (MW) of FeFETs reported so far is rather limited, which might be an obstacle to practical applications. In this article, we report on FeFETs fabricated in the 28-nm high-𝑘 metal gate (HKMG) bulk technology with 90 and 80 nm for the channel length and width, respectively, which show a large MW of nearly 3 V. This is achieved by adopting 20-nm-thick HfO₂ films in the gate stack instead of the usually employed 10-nm-thick films. We show that such a thickness increase leads to only a moderate increase of the switching voltages, and to a significantly improved resilience of the memory characteristics upon the parasitic charge trapping. The devices display a good retention at high temperatures and endure more than 10⁵ bipolar cycles, thus supporting this technology for a future generation of FeFET memories.

Despite increasing attention for the recently found ferro- and antiferroelectric properties, the polymorphism in hafnia- and zirconia-based thin films is still not sufficiently understood. In the present work, we show that it is important to have a good quality X-ray absorption spectrum to go beyond an analysis of the only the first coordination shell. Equally important is to analyze both EXAFS and XANES spectra in combination with theoretical modelling to distinguish the relevant phases even in bulk materials and to separate structural from chemical effects. As a first step toward the analysis of thin films, we start with the analysis of bulk references. After that, we successfully demonstrate an approach that allows us to extract high-quality spectra also for 20 nm thin films. Our analysis extends to the second coordination shell and includes effects created by chemical substitution of Hf with Zr to unambiguously discriminate the different polymorphs. The trends derived from X-ray absorption spectroscopy agree well with X-ray diffraction measurements. In this work we clearly identify a gradual transformation from monoclinic to tetragonal phase as the Zr content of the films increases. We separated structural effects from effects created by chemical disorder when ration of Hf:Zr is varied and found differences for the incorporation of the substitute atoms between powders and thin films, which we attribute to the different fabrication routes. This work opens the door for further in-depth structural studies to shine light into the chemistry and physics of these novel ferroelectric thin films that show high application relevance.