Roadmap on ferroelectric hafnia- and zirconia-based materials and devices

Ferroelectric hafnium and zirconium oxides have undergone rapid scientific development over the last decade, pushing them to the forefront of ultralow-power electronic systems. Maximizing the potential application in memory devices or supercapacitors of these materials requires a combined effort by the scientific community to address technical limitations, which still hinder their application. Besides their favorable intrinsic material properties, HfO2–ZrO2 materials face challenges regarding their endurance, retention, wake-up effect, and high switching voltages. In this Roadmap, we intend to combine the expertise of chemistry, physics, material, and device engineers from leading experts in the ferroelectrics research community to set the direction of travel for these binary ferroelectric oxides. Here, we present a comprehensive overview of the current state of the art and offer readers an informed perspective of where this field is heading, what challenges need to be addressed, and possible applications and prospects for further development

Pyroelectric and electrocaloric effects in hafnium oxide thin films

The material class of hafnium oxide-based ferroelectrics adds an unexpected and huge momentum to the long-known phenomenon of pyroelectricity. In this thesis, a comprehensive study of pyroelectric and electrocaloric properties of this novel ferroelectric material class is conducted. hafnium oxide is a lead-free, non-toxic transition metal oxide, and abundant in the manufacturing of semiconductor devices. The compatibility to existing fabrication processes spawns the possibility of on-chip infrared sensing, energy harvesting, and refrigeration solutions, for which this dissertation aims to lay a foundation. A screening of the material system with respect to several dopants reveals an enhanced pyroelectric response at the morphotropic phase boundary between the polar orthorhombic and the non-polar tetragonal phase. Further, a strong pyroelectric effect is observed when applying an electric field to antiferroelectric-like films, which is attributed to a field-induced transition between the tetragonal and orthorhombic phases. Primary and secondary pyroelectric effects are separated using high-frequency temperature cycles, where the effect of frequency-dependent substrate clamping is exploited. The piezoelectric response is determined by comparing primary and secondary pyroelectric coefficients, which reproduces the expected wake-up behavior in hafnium oxide films. Further, the potential of hafnium oxide for thermal-electric energy conversion is explored. The electrocaloric temperature change of only 20 nm thick films is observed directly by using a specialized test structure. By comparing the magnitude of the effect to the pyroelectric response, it is concluded that defect charges have an important impact on the electrocaloric effect in hafnium oxide-based ferroelectrics. Energy harvesting with a conformal hafnium oxide film on a porous, nano-patterned substrate is performed, which enhances the power output. Further, the integration of a pyroelectric energy harvesting device in a microchip for waste heat recovery and more energy-efficient electronic devices is demonstrated. High dielectric breakdown fields of up to 4 MV/cm in combination with a sizable pyroelectric response and a comparably low dielectric permittivity illustrate the prospect of hafnium oxide-based devices for future energy conversion applications

High‐Performance Zinc Tin Oxide TFTs with Active Layers Deposited by Atomic Layer Deposition

New deposition techniques for amorphous oxide semiconductors compatible with silicon back end of line manufacturing are needed for 3D monolithic integration of thin‐film electronics. Here, three atomic layer deposition (ALD) processes are compared for the fabrication of amorphous zinc tin oxide (ZTO) channels in bottom‐gate, top‐contact n‐channel transistors. As‐deposited ZTO films, made by ALD at 150–200 °C, exhibit semiconducting, enhancement‐mode behavior with electron mobility as high as 13 cm2 V−1 s−1, due to a low density of oxygen‐related defects. ZTO deposited at 200 °C using a hybrid thermal‐plasma ALD process with an optimal tin composition of 21%, post‐annealed at 400 °C, shows excellent performance with a record high mobility of 22.1 cm2 V–1 s–1 and a subthreshold slope of 0.29 V dec–1. Increasing the deposition temperature and performing post‐deposition anneals at 300–500 °C lead to an increased density of the X‐ray amorphous ZTO film, improving its electrical properties. By optimizing the ZTO active layer thickness and using a high‐k gate insulator (ALD Al2O3), the transistor switching voltage is lowered, enabling electrical compatibility with silicon integrated circuits. This work opens the possibility of monolithic integration of ALD ZTO‐based thin‐film electronics with silicon integrated circuits or onto large‐area flexible substrates.Three atomic layer deposition (ALD) processes are investigated for the deposition of zinc tin oxide (ZTO) as the active layer in thin‐film transistors (TFTs). With a low density of oxygen vacancies, as‐deposited films exhibit semiconducting, enhancement‐mode behavior. Post‐deposition anneals result in increased film density and record high electron mobility for ALD ZTO TFTs using process temperatures within the back‐end‐of‐line thermal budget.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/156226/3/aelm202000195-sup-0001-SuppMat.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156226/2/aelm202000195.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156226/1/aelm202000195_am.pd

Optimization of performance and reliability of HZO-based capacitors for ferroelectric memory applications

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

Coatings for ALD Reactors to Prevent Metal Contamination on Semiconductor Products

Atomic layer deposition (ALD) is a promising processing method for the next generation semiconductor devices. Major advantages of ALD include conformality, uniformity over large areas, precise thickness control, repeatability and high quality of films produced. ALD thin film deposition is done inside an ALD reactor. Typical construction materials of ALD reactors include metal alloys such as stainless steel, aluminum and titanium. These materials contain multiple metallic elements that can be detrimental to the performance, reliability and yield of semiconductor devices. In order to process semiconductor devices with ALD, metal impurity levels originating from the ALD reactor must be controlled. Allowed levels of metal impurities in semiconductor processing are stringent and showing a tightening trend. This has led into the development of new methods for contamination control together with the adoption of more sensitive and robust detection methods for metallic impurities, such as inductively coupled plasma mass spectrometry (ICP-MS). This master thesis focuses on the metallic impurities originating from an ALD reactor and their prevention with ALD coatings. Three typical construction materials, aluminum, titanium and stainless steel were examined. The studied coatings were ALD deposited aluminum oxide (Al2O3), hafnium oxide (HfO2) and their nanolaminate (Al2O3/HfO2). The ability of the coatings to prevent metal impurity transfer from the metals to silicon substrates through the gas phase was studied by exposing the coated metals to two ALD precursors, trimethyl aluminum (TMA) and tris(dimethylamino) cyclopentadienyl hafnium (CpHf(NMe2)3). Metal impurity concentrations on silicon were measured with ICP-MS. Since academic literature concerning control of metal contamination from ALD reactors does not directly exist, the literature part of this thesis was based on relevant related topics. The selected topics included the development of semiconductor industry, role of ALD in this development and new ALD materials and chemistries required. Additionally, protective ALD films and the effects of metal impurities in semiconductor products were reviewed. The overall conclusion of this study was that the ALD coatings provide a worthy solution for metal contamination control. Some differences between the passivation efficiencies of different metal – coating systems were found

An investigation of high-k materials in metal-insulator-metal capacitor structures

Metal insulator metal (MIM) capacitors are vital components of many devices such as communication band beamformers, medical, automotive, RF IC’s and memory applications. Current MIM capacitors technology utilises low dielectric constant (k) materials (k~3.9 - 7), these materials achieve the required electrical properties of high electric field breakdown strength and minimal leakage current. The low k value of the current materials presents a challenge to development of many new technologies and the integration of high-k materials in MIM capacitor structures is vital to overcome this. In this work we investigate the electrical properties of a hafnium silicate material system in MIM capacitors with sputtered aluminium electrodes. A conduction mechanism study was performed and an investigation of the dielectric reliability was carried out using the time dependent dielectric breakdown methodology. The material was determined to have excellent reliability characteristics. In addition, further samples of the above hafnium silicate capacitors were irradiated with total radiation dosages of 16 krad(Si) and 78 krad(Si). The electrical properties of both samples were characterised and their reliability characteristics were determined. The 16 krad(Si) sample was determined to have excellent radiation hardness and the 78 krad(Si) sample displayed a minor decrease in overall performance. Furthermore, we investigate the growth of hafnium silicate films by plasma assisted atomic layer deposition on metal electrodes and compare with a previous growth study which exhibited excellent electrical properties over a range of substrate materials. In this study the dielectric growth was influenced by the bottom electrode material. High resolution transmission electron microscopy (HRTEM) analysis and Raman spectroscopy indicate that the main crystalline phase is monoclinic HfO2 (k ~18). The scanning transmission electron microscopy (STEM) analysis reveals the presence of nanoparticles, located at the HfO2 grain boundaries. Based on energy-dispersive x-ray spectroscopy (EDX) analysis the nanoparticles are consistent with silicon oxide inclusions

Material development of doped hafnium oxide for non-volatile ferroelectric memory application

Seit der Entdeckung von Ferroelektrizität in Hafniumoxid stellt es aufgrund seiner Prozesskompatibilität im Bereich der Mikroelektronik sowie seiner besonderen Eigenschaften ein wachsendes Forschungsfeld dar. Im Speziellen wird die Anwendung in nicht-flüchtigen Speichern, in neuromorphen Bauelementen sowie in piezo-/pyroelektrischen Sensoren untersucht. Jedoch ist das Verhalten von ferroelektrischem Hafniumoxid im Vergleich zu Ferroelektrika mit Perovskit-Struktur nicht im Detail verstanden. Zudem spielen Prozesseinflüsse während und nach der Abscheidung eine entscheidende Rolle für die Materialeigenschaften aufgrund der metastabilen Natur der ferroektrischen Phase in diesem Materialsystem. In dieser Arbeit werden die grundlegenden physikalischen Eigenschaften von Hafniumoxid, Prozesseinflüsse auf die Mikrostruktur und Zuverlässigkeitsaspekte von nicht-flüchtigen sowie neuromorphen Bauelementen untersucht. Im Bezug auf die physikalischen Eigenschaften zeigen sich hier deutliche Belege für ferroelastische 90° Domänenwandbewegungen in Hafniumoxid-basierten Dünnschichten, welche in einem ähnlichen Verhalten wie ein Antiferroelektrikum resultieren. Weiterhin wird über die Entdeckung von einer mittels elektrischem Feld induzierten Kristallisation in diesem Materialsystem berichtet. Für die Charakterisierung der Mikrostruktur wird als neue Methode Transmissions-Kikuchi-Diffraktion eingeführt, welche eine detaillierte Untersuchung der lokalen kristallographischen Phase, Orientierung und Gefügestruktur ermöglicht. Hierbei zeigen sich deutliche Vorzugsorientierungen in Abhängigkeit des Substrates, der Dotierstoffkonzentration sowie der Glühtemperatur. Auf Basis dieser Ergebnisse lassen sich die beobachteten Zuverlässigkeitsverhalten in Bauelementen erklären und mittels Defektkontrolle weiter optimieren. Schließlich wird das Verhalten in neuromorphen Bauelementen untersucht und Leitlinien für Prozess- und Bauelementoptimierung gegeben.:Abstract i Abstract ii List of Figures vi List of Tables x Acronyms xi Symbols xiv 1 Introduction 1 2 Theoretical background 3 2.1 Behavior of ferroelectric materials 3 2.1.1 Phase transitions at the Curie temperature 4 2.1.2 Domains, domain walls, and microstructure 5 2.2 Ferroelectricity in HfO2 6 2.2.1 Thermodynamics and kinetics 8 2.2.2 Antiferroelectric-like behavior, wake-up effect, and fatigue 11 2.2.3 Piezo- and pyroelectric effects 13 2.3 Ferroelectric FETs 13 2.3.1 Endurance, retention and variability 14 2.3.2 Neuromorphic devices 15 3 Methodology 17 3.1 Electrical analysis 17 3.1.1 Capacitors 17 3.1.2 FeFETs 19 3.2 Structural and chemical analysis 20 3.2.1 Grazing-incident X-ray diffraction (GIXRD) 20 3.2.2 Transmission electron microscopy (TEM) 20 3.2.3 Time-of-flight secondary ion mass spectrometry (ToF-SIMS) 21 3.3 Transmission Kikuchi diffraction 21 3.4 Sample preparation 23 4 The physics of ferroelectric HfO2 25 4.1 Ferroelastic switching 25 4.2 Electric field-induced crystallization 30 5 Microstructure engineering 33 5.1 Microstructure and ferroelectric domains in HfO2 33 5.2 Doping influences 34 5.2.1 Zr doping (similar ionic radius) 35 5.2.2 Si doping (smaller ionic radius) 43 5.2.3 La doping (larger ionic radius) 50 5.2.4 Co-doping 50 5.3 Annealing influences 53 5.4 Interlayer influences 58 5.5 Interface layer influences 62 5.5.1 Structural differences in the HfO2 layer 63 5.5.2 Interactions of the interface and HfO2 layer 67 5.5.3 Substrate-driven changes in the Si-doping profile 73 5.6 Phenomenological wake-up behaviors and process guidelines 77 6 HfO2-based ferroelectric FETs 81 6.1 Endurance, retention and variability 81 6.1.1 Analytic model of HfO2-based FeFETs 84 6.1.2 Endurance improvements by interface fluorination 94 6.2 Neuromorphic devices and circuits 98 6.2.1 Current peroclation paths in FeFETs 100 6.2.2 Material and stack influences on synaptic devices 105 6.2.3 Reliability aspects of synaptic devices 106 7 Conclusion and outlook 109 Appendix 142 Density-functional-theory calculations 142 Supplementary Figures 143 Publications 145 Acknowledgment 156 Declaration 158The discovery of ferroelectricity in hafnium oxide spurred a growing research field due to hafnium oxides compatibility with processes in microelectronics as well as its unique properties. Notably, its application in non-volatile memories, neuromorphic devices as well as piezo- and pyroelectric sensors is investigated. However, the behavior of ferroelectric hafnium oxide is not understood into depth compared to common perovskite structure ferroelectrics. Due the the metastable nature of the ferroelectric phase, process conditions have a strong influence during and after its deposition. In this work, the physical properties of hafnium oxide, process influences on the microstructure as well as reliability aspects in non-volatile and neuromorphic devices are investigated. With respect to the physical properties, strong evidence is provided that the antiferroelectric-like behavior in hafnium oxide based thin films is governed by ferroelastic 90° domain wall movement. Furthermore, the discovery of an electric field-induced crystallization process in this material system is reported. For the analysis of the microstructure, the novel method of transmission Kikuchi diffraction is introduced, allowing an investigation of the local crystallographic phase, orientation and grain structure. Here, strong crystallographic textures are observed in dependence of the substrate, doping concentration and annealing temperature. Based on these results, the observed reliability behavior in the electronic devices is explainable and engineering of the present defect landscape enables further optimization. Finally, the behavior in neuromorphic devices is explored as well as process and design guidelines for the desired behavior are provided.:Abstract i Abstract ii List of Figures vi List of Tables x Acronyms xi Symbols xiv 1 Introduction 1 2 Theoretical background 3 2.1 Behavior of ferroelectric materials 3 2.1.1 Phase transitions at the Curie temperature 4 2.1.2 Domains, domain walls, and microstructure 5 2.2 Ferroelectricity in HfO2 6 2.2.1 Thermodynamics and kinetics 8 2.2.2 Antiferroelectric-like behavior, wake-up effect, and fatigue 11 2.2.3 Piezo- and pyroelectric effects 13 2.3 Ferroelectric FETs 13 2.3.1 Endurance, retention and variability 14 2.3.2 Neuromorphic devices 15 3 Methodology 17 3.1 Electrical analysis 17 3.1.1 Capacitors 17 3.1.2 FeFETs 19 3.2 Structural and chemical analysis 20 3.2.1 Grazing-incident X-ray diffraction (GIXRD) 20 3.2.2 Transmission electron microscopy (TEM) 20 3.2.3 Time-of-flight secondary ion mass spectrometry (ToF-SIMS) 21 3.3 Transmission Kikuchi diffraction 21 3.4 Sample preparation 23 4 The physics of ferroelectric HfO2 25 4.1 Ferroelastic switching 25 4.2 Electric field-induced crystallization 30 5 Microstructure engineering 33 5.1 Microstructure and ferroelectric domains in HfO2 33 5.2 Doping influences 34 5.2.1 Zr doping (similar ionic radius) 35 5.2.2 Si doping (smaller ionic radius) 43 5.2.3 La doping (larger ionic radius) 50 5.2.4 Co-doping 50 5.3 Annealing influences 53 5.4 Interlayer influences 58 5.5 Interface layer influences 62 5.5.1 Structural differences in the HfO2 layer 63 5.5.2 Interactions of the interface and HfO2 layer 67 5.5.3 Substrate-driven changes in the Si-doping profile 73 5.6 Phenomenological wake-up behaviors and process guidelines 77 6 HfO2-based ferroelectric FETs 81 6.1 Endurance, retention and variability 81 6.1.1 Analytic model of HfO2-based FeFETs 84 6.1.2 Endurance improvements by interface fluorination 94 6.2 Neuromorphic devices and circuits 98 6.2.1 Current peroclation paths in FeFETs 100 6.2.2 Material and stack influences on synaptic devices 105 6.2.3 Reliability aspects of synaptic devices 106 7 Conclusion and outlook 109 Appendix 142 Density-functional-theory calculations 142 Supplementary Figures 143 Publications 145 Acknowledgment 156 Declaration 15

Integration of Ferroelectric HfO2 onto a III-V Nanowire Platform

The discovery of ferroelectricity in CMOS-compatible oxides, such as doped hafnium oxide, has opened new possibilities for electronics by reviving the use of ferroelectric implementations on modern technology platforms. This thesis presents the ground-up integration of ferroelectric HfO2 on a thermally sensitive III-V nanowire platform leading to the successful implementation of ferroelectric transistors (FeFETs), tunnel junctions (FTJs), and varactors for mm-wave applications. As ferroelectric HfO2 on III-V semiconductors is a nascent technology, a special emphasis is put on the fundamental integration issues and the various engineering challenges facing the technology.The fabrication of metal-oxide-semiconductor (MOS) capacitors is treated as well as the measurement methods developed to investigate the interfacial quality to the narrow bandgap III-V materials using both electrical and operando synchrotron light source techniques. After optimizing both the films and the top electrode, the gate stack is integrated onto vertical InAs nanowires on Si in order to successfully implement FeFETs. Their performance and reliability can be explained from the deeper physical understanding obtained from the capacitor structures.By introducing an InAs/(In)GaAsSb/GaSb heterostructure in the nanowire, a ferroelectric tunnel field effect transistor (ferro-TFET) is fabricated. Based on the ultra-short effective channel created by the band-to-band tunneling process, the localized potential variations induced by single ultra-scaled ferroelectric domains and individual defects are sensed and investigated. By intentionally introducing a gate-source overlap in the ferro-TFET, a non-volatile reconfigurable single-transistor solution for modulating an input signal with diverse modes including signal transmission, phase shift, frequency doubling, and mixing is implemented.Finally, by fabricating scaled ferroelectric MOS capacitors in the front-end with a dedicated and adopted RF and mm-wave backend-of-line (BEOL) implementation, the ferroelectric behavior is captured at RF and mm-wave frequencies