Les matériaux conducteurs de basse dimensionnalité électronique peuvent présenter des transitions vers des états électroniques complexes tels que la supraconduction, les Ondes de Densité de Spins (ODS) et les Ondes de Densité de Charges (ODC). La coexistence de plusieurs de ces instabilités au sein d’un même matériau a donné lieu à une recherche active de nouveaux systèmes conducteurs quasi-bidimensionnels. Dans cette thèse nous avons choisi de nous intéresser à la famille des Bronzes MonoPhosphate de Tungstène à tunnels pentagonaux (MPTBp), de formule chimique (PO2)4(WO3)2m ; l’un des principaux intérêts réside dans la possibilité de contrôler directement la dimensionnalité du matériau et sa densité de porteurs en faisant varier la valeur de m (2 ≤ m ≤ 14). Dans la littérature il a été montré que certains termes de cette famille (m=4, 5, 6) admettent des états ODC successifs alors que d’autres (m=10) présentent des ordres de type ferro électrique ; l’objectif de cette thèse est alors de montrer l’effet de la dimensionnalité du matériau sur l’apparition et la stabilité de ces états électroniques dans les MPTBp. Pour cela, des mesures de transport électronique, des études des structures modulées incommensurables et commensurables par diffraction des rayons X avant et après chaque transition et des mesures de diffusion inélastique ont été effectuées sur plusieurs termes à valeur de m pair. Dans ce travail nous avons pu montrer l’existence d’un état ODC pour les termes m=2, 4, 6, 8 et 10, caractérisé par la formation d’amas de tungstène dans certaines régions du matériau, accompagné, pour les m=8 et 10, de l’installation progressive d’une mise en ordre de type anti-ferroélectrique des déplacements des atomes de tungstène. Un phénomène de dépiégeage d’ODC a été observé pour le terme quasi-unidimensionnel m=2, ce qui n’avait encore jamais été reporté chez les MPTBp. Un couplage électron-phonon fort a pu être mis en évidence pour les hauts termes (m ≥ 8) à la fois via les analyses structurales, l’observation de transitions résistives du premier ordre mais également par des mesures de diffusion inélastique des rayons X. Pour ces hauts termes, une transition de type ordre-désordre est alors à envisager. / Conductive materials with low electronic dimensionality can present some transitions toward complex electronic states as superconductivity, Spin Density Waves (SDW) and Charge Density Waves (CDW). The coexistence of several of these instabilities in the same material leads to bustling investigations on new quasi-bidimensional conductors. In this thesis, we chose to study the MonoPhosphate Tungsten Bronzes with pentagonal channels family (MPTBp), of chemical formula (PO2)4(WO3)2m ; one of the main interests of this family is the possibility to directly control the compound’s dimensionality and its carriers density by varying m value (2 ≤ m ≤ 14). In the literature, it’s been shown that some MPTBp members (m=4, 5, 6) present successive CDW states whereas others (m=10) show ferroelectric-type orders. The aim of this thesis is thus to bring into light the effect of the material’s dimensionality on the appearance and the stability of these electronic states in the MPTBp family. In this way, transport measurements, X-Rays diffraction studies of the commensurate and incommensurate modulated structures below and above each transition and inelastic scattering measurements were done on several members with even value of m. In this work we reveal the existence of a CDW state for the m=2, 4, 6, 8 and 10 members, characterized by the formation of tungsten clusters in some areas of the crystal. For the m=8 and 10 members, the CDW is accompanied by a gradual installation of an anti-ferroelectric-like ordering of the tungsten atoms displacements. A CDW depinning phenomenon was observed for the quasi-unidimensional m=2 member, which has never been reported before in the MPTBp family. A strong electron-phonon coupling was evidenced for the high terms of the family (m ≥ 8) by structural analysis, first order resistive transitions observation and by X-Rays inelastic scattering measurements. For these high terms, an order-disorder transition must be considered.

Ferroelectricity in hafnium oxide thin films is known to be induced by various doping elements and in solid-solution with zirconia. While a wealth of studies is focused on their basic ferroelectric properties and memory applications, thorough studies of the related pyroelectric properties and their application potential are only rarely found. This work investigates the impact of Si doping on the phase composition and ferro- as well as pyroelectric properties of thin film capacitors. Dynamic hysteresis measurements and the field-free Sharp-Garn method were used to correlate the reported orthorhombic phase fractions with the remanent polarization and pyroelectric coefficient. Maximum values of 8.21 µC cm−2 and −46.2 µC K−1 m−2 for remanent polarization and pyroelectric coefficient were found for a Si content of 2.0 at%, respectively. Moreover, temperature-dependent measurements reveal nearly constant values for the pyroelectric coefficient and remanent polarization over the temperature range of 0 °C to 170 °C, which make the material a promising candidate for IR sensor and energy conversion applications beyond the commonly discussed use in memory applications.

To overcome the fundamental limit of the transistor subthreshold swing of 60 mV/dec at room temperature, the use of negative capacitance (NC) in ferroelectric materials was proposed [1]. Due to the recent discovery of ferroelectricity in CMOS compatible HfO₂ and ZrO₂ based thin films [2], [3], the promise of ultra-low power steep-slope devices seems within reach. However, concerns have been raised about switching-speed limitations and unavoidable hysteresis in NC devices [4], [5]. Nevertheless, it was shown that NC effects without hysteresis can be observed in fast pulsed voltage measurements on ferroelectric/dielectric capacitors [6], which was recently confirmed using ferroelectric Hf₀.₅ Zr₀.₅ O₂[7], [8]. While in these works only the integrated charge after each pulse was studied, here we investigate for the first time if the transient voltage and charge characteristics are also hysteresis-free.

Thin film metal–insulator–metal capacitors with undoped HfO₂ as the insulator are fabricated by sputtering from ceramic targets and subsequently annealed. The influence of film thickness and annealing temperature is characterized by electrical and structural methods. After annealing, the films show distinct ferroelectric properties. Grazing incidence X-ray diffraction measurements reveal a dominant ferroelectric orthorhombic phase for thicknesses in the 10–50 nm range and a negligible non-ferroelectric monoclinic phase fraction. Sputtering HfO₂ with additional oxygen during the deposition decreases the remanent polarization. Overall, the impact of oxygen vacancies and interstitials in the HfO₂ film during deposition and annealing is correlated to the phase formation process.

This article corrects the following: 'Origin of Ferroelectric Phase in Undoped HfO2 Films Deposited by Sputtering' Advanced Materials Interfaces 6(11) 2019, first Published online: April 29, 2019

The ferroelectricity in fluorite-structure oxides such as hafnia and zirconia has attracted increasing interest since 2011. They have various advantages such as Si-based complementary metal oxide semiconductor-compatibility, matured deposition techniques, a low dielectric constant and the resulting decreased depolarization field, and stronger resistance to hydrogen annealing. However, the wake-up effect, imprint, and insufficient endurance are remaining reliability issues. Therefore, this paper reviews two major aspects: the advantages of fluorite-structure ferroelectrics for memory applications are reviewed from a material’s point of view, and the critical issues of wake-up effect and insufficient endurance are examined, and potential solutions are subsequently discussed.

Gegenstand dieser Arbeit ist die experimentelle Untersuchung der Verspannungs-Temperatur-Phasenbeziehungen in epitaktischen KxNa1-xNbO3 Dünnschichten, sowie deren Zusammenhang mit ferro- und piezoelektrischen Eigenschaften. Die präsentierten Ergebnisse ermöglichen es KxNa1-xNbO3 Dünnschichten für neuartige technologische Anwendung zu optimieren. Zunächst wird eine detaillierte strukturelle Untersuchung der ferroelektrischen Domänenstruktur in epitaktischen K0.7Na0.3NbO3 Schichten auf (110) TbScO3 vorgestellt. Eine Analyse der ferroelektrischen Domänenstruktur mittels lateral aufgelöster Piezoresponse-Kraftmikroskopie (PFM) zeigt vier Arten von Superdomänen. Durch die ergänzende Untersuchung der zweidimensionalen und dreidimensionalen Abbildung des reziproken Raumes mittels hochauflösender Röntgenbeugung (HR-XRD) wird nachgewiesen, dass dieses Domänenmuster mittels monokliner Einheitszellen in einem MC Domänenmodell beschrieben werden kann. Im Anschluss an die strukturelle Untersuchung wurden die elektromechanischen Eigenschaften der KxNa1-xNbO3 Schichten auf (110) TbScO3untersucht. Mittels Doppelstrahl-Laserinterferometrie (DBLI) wurde ein makroskopischer effektiver piezoelektrischer Koeffizient von bis zu d33,f = 23 pm/V nachgewiesen. Zudem wurden Oberflächenwellen-Experimente (SAW) durchgeführt. Diese zeigten außergewöhnlich hohe Signalstärken. Um die Temperatur der ferroelektrischen Phasenübergänge gezielt einstellen zu können, wurde der Zusammenhang zwischen epitaktischer Verspannung und der Phasenübergangstemperatur untersucht. Dazu wurden KxNa1-xNbO3 Schichten mit unterschiedlicher Verspannung gewachsen. Die Änderung der Domänenstruktur und der piezoelektrischen Eigenschaften aufgrund von Temperaturänderung wurde in-situ durch temperaturabhängige PFM, HR-XRD und DBLI Messungen untersucht. Die Untersuchung zeigte, dass die Übergangstemperatur des Übergangs von der MC- in die c-Phase mit zunehmender kompressiver Verspannung kontinuierlich um mehr als 400 °C abnahm. / The subject of this thesis is the experimental investigation of the strain-temperature-phase relations in epitaxial KxNa1-xNbO3 thin films and their connection to ferro- and piezoelectric properties. This will enable the optimization of KxNa1-xNbO3 layers for novel technological devices. First, a detailed structural investigation of the ferroelectric domain structure in epitaxial K0.7Na0.3NbO3 films on (110) TbScO3 is presented. An analysis of the ferroelectric domain structure with laterally resolved piezoresponse force microscopy (PFM) reveals four types of superdomains. By complementary two-dimensional and three-dimensional high resolution X-ray reciprocal space mapping this domain pattern is proven to be describable by an MC domain structure with monoclinic unit cells. Subsequently to the structural investigation, the electromechanical properties of KxNa1-xNbO3 layers on (110) TbScO3 were investigated. Double beam laser interferometry (DBLI) revealed a macroscopic effective piezoelectric coefficient of up to d33,f = 23 pm/V. Furthermore, surface acoustic wave (SAW) experiments were performed. They exhibited extraordinary signal intensities. In order to be able to selectively tune such phase transition temperatures, the correlation between epitaxial strain and the phase transition temperature was investigated. For this purpose, KxNa1-xNbO3 films with different compressive strain conditions were grown. The change of domain structure and piezoelectric properties upon temperature variation was investigated in-situ by temperature-dependent PFM, HR-XRD and DBLI measurements. The transition temperature between the MC- and c-phase was shown to continuously decrease by more than 400 °C with increasing compressive strain.

The ferroelectricity in fluorite oxides has gained increasing interest due to its promising properties for multiple applications in semiconductor as well as energy devices. The structural origin of the unexpected ferroelectricity is now believed to be the formation of a non-centrosymmetric orthorhombic phase with the space group of Pca2₁. However, the factors driving the formation of the ferroelectric phase are still under debate. In this study, to understand the effect of annealing temperature, the crystallization process of doped HfO₂ thin films is analyzed using in situ, high-temperature X-ray diffraction. The change in phase fractions in a multiphase system accompanied with the unit cell volume increase during annealing could be directly observed from X-ray diffraction analyses, and the observations give an information toward understanding the effect of annealing temperature on the structure and electrical properties. A strong coupling between the structure and the electrical properties is reconfirmed from this result.

Nonlinear optics and ferroelectrics have been recognized for several decades as promising fields with important applications in the area of opto-electronics, photonics, memory devices, etc. High performance electro-optical switching elements for telecommunications and optical information processing are based on the material properties. Hence, there is always a continuous search for new and better materials. In this thesis we have investigated the growth and physical properties of four crystals viz. two NLO and two ferroelectric crystals. This thesis consists of eight chapters. The first chapter gives an overview of historical perspectives of nonlinear optical phenomenon, ferroelectricity and materials developed therein. The second chapter gives a brief description of the underlying theories of crystal growth, nonlinear optics and ferroelectricity. A major portion of this chapter consists of gist of the earlier work carried out on compounds of our interest viz. urea L-malic acid, sodium p-nitrophenolate dihydrate, glycine phosphite and lithium niobate. Synthesis, growth, crystal structure details and some physical properties of these materials are briefed. The third chapter describes the experimental techniques needed to grow as well as characterize these crystals. The experiments are performed on single crystals grown in the laboratory using the solution growth setup and Czochralski crystal puller. These growth units are described in detail. Preliminary characterization techniques like powder Xray diffraction, optical transmission, scanning electron microscopy, Vickers and Knoop hardness are described briefly. Various experimental methods viz. dielectric, polarization reversal, photoacoustic spectroscopy and laser induced damage for characterizing the grown crystals are explained. Urea L-malic acid (ULMA) is a new NLO organic material which is reported to exhibit second harmonic efficiency three times that of the widely used inorganic crystal, KDP. Hence, this material is selected for detailed investigation and the results obtained are discussed in chapter 4. This chapter contains details of single crystal growth and characterization of ULMA. The crystals are grown by slow cooling technique. The complete morphology of the crystal is evaluated using optical goniometry. The grown crystals are characterized for their optical and thermal properties. The defect content in the grown crystal is evaluated by chemical etching. As the surface damage of the crystal by high power lasers limits its performance in NLO applications, a detailed laser induced damage studies are performed on ULMA. Both single shot and multiple shot damage threshold values for 1064 nm and 532 nm laser radiation are determined and correlated with the mechanical hardness. In addition, the thermal diffusivity and thermal conductivity of ULMA along various crystallographic orientations are evaluated using laser induced photoacoustic spectroscopy and the results are interpreted in terms of crystal bonding environment. Another NLO crystal taken up for study is sodium p-nitrophenolate dihydrate (NPNa 2H2O), a semiorganic material. This crystal is a very efficient NLO material and has the advantages of both organics and inorganics. Earlier investigations on growth of NPNa.2H2O in various solvents have shown methanol as the most suitable solvent for growth. Growth from aqueous solution was discarded as it did not yield crystals which are stable. In the present investigation, stable, NLO active NPNa.2H2O crystals are obtained using aqueous solution itself by varying the crystallization conditions and exploring the suitable temperature range. The details of growth and characterization form the subject of fifth chapter. The grown crystals are characterized using optical transmission, XRD and thermo gravimetric analysis. Later, laser induced damage threshold is evaluated for both 1064 nm and 532 nm laser radiation and compared wit the methanol grown ones. A possible mechanism of damage is given. The sixth and seventh chapters deal with growth and characterization of ferroelectric materials namely glycine phosphite and lithium niobate respectively. Glycine phosphite is a low temperature ferroelectric crystal which is well studied in terms of its dielectric and ferroelectric properties. But very few radiation damage studies are reported. The effect of ionizing radiation on ferroelectrics is of considerable interest as it significantly modifies the physical properties of these materials. In the present investigation, effects of X-ray irradiation (_ = 1.5418 °A) on the lattice parameters, dielectric constant, loss tangent, polarization switching characteristics and domain dynamics of glycine phosphite are investigated. X-ray irradiation is performed in the non-polar phase of the sample. The effect as a function of duration of exposure is studied. X-ray irradiation in GPI has resulted in drastic reduction in _ values and shift in transition temperature towards lower temperatures. X-ray irradiation on polarization switching properties of the crystal are also investigated. The activation energy and threshold field of switching increase with the irradiation time. The behaviour of domain wall mobility is quite different from that exhibited by other well known ferroelectrics. These results are discussed in chapter 6 and a possible explanation for the unusual behaviour of domain wall mobility is given. The defect generated is identified as PO32− radical by electron paramagnetic measurement. Lithium niobate (LiNbO3) is an extensively studied material in terms of its NLO and ferroelectric properties. This material has high piezoelectric coupling coefficients along certain directions which makes it suitable for wide band surface acoustic wave applications. Hence there is a demand for good quality, single domain YZ-LiNbO3 substrates. Chapter 7 describes the growth of Z-pulled congruent LiNbO3 using Czochralski technique. Large single crystals of diameter 30 mm and length 80 mm are grown from congruent composition employing Czochralski technique. The grown crystals are multidomain and hence electric field poling is performed to get single domain crystals. Their subsequent characterization for SAW devices upto 200 MHz was performed and compared with the imported substrate. The general conclusions are given in chapter 8 along with possible future work that could be performed on these crystals.

Fabrication of artificially structured superlattices, when controlled on a nanoscale level, can exhibit enhanced dielectric properties over a wide temperature range. Possible fabrication of new functional devices based on the parametric values of dielectric constants of these heterostructures was the major motivation behind the work. Chapter 1 gives a brief overview of ferroelectrics; their defining features and their commercial importance to electronic industry. An introduction to ferroelectric superlattices, their technological application and fundamental physics that influence the behavior of superlattices are provided. Chapter 2 deals with the various experimental studies carried out in this research work. It gives the details of the experimental set up and the basic operation principles of various structural and physical characterizations of the materials prepared. A brief explanation of material fabrication, structural, micro structural and physical property measurements is discussed. Chapter 3 involves fabrication of two-component ferroelectric superlattices consisting of Barium Titanate (BTO), and Strontium Titanate (STO) with nanoscale control of superlattice periodicities by high-pressure multi target pulsed laser deposition on Pt (111)/Ti/SiO2/Si (100) substrate. Superlattices with varying periodicities were fabricated and their compositional variation across the thin film and the interface width were studied using Secondary Ion Mass Spectrometry (SIMS). Fabrications of superlattice structure were supported by observation of satellite peaks in XRD corresponding to the coherent heterostructures. The microstructural analysis was carried out using cross-sectional scanning electron microscopy (SEM), and contact mode-AFM was used to image surface morphology and root-mean-square (rms) roughness of the thin film heterostructure. Chapter 4 deals with ferroelectric studies of BTO/STO superlattices. The size dependent polarization behaviors of the superlattices are shown. The experimental realization of the dimensional range in which, the long-range coupling interaction dominates the overall polarization behavior of the system was studied. The dependence of average spontaneous polarization on the individual layer thickness, temperature and the dimensional range of interaction are discussed. The enhanced non-linear behaviors of the films were measured in terms of tunability. The dielectric phase transition behavior of superlattice structures of different periodicities was studied. Chapter 5 focuses on fabrication of three-component ferroelectric superlattices consisting of Barium Titanate (BTO), Calcium Titanate (CTO) and Strontium Titanate (STO). The fabrications of superlattice structures were confirmed by the presence of satellite reflections in XRD analysis and a periodic concentration of Sr, Ba and Ca throughout the film in Depth profile of SIMS analysis. The microstructural analysis was carried out using cross-sectional scanning electron microscopy (SEM), and contact mode-AFM was used to image surface morphology and root-mean-square (rms) roughness of the thin film heterostructure. The dielectric characteristic and polarization properties of the system are discussed. Large variations of lattice distortion in the consisting layers were achieved by varying the stacking sequence and superlattice periodicity. The influence of interfacial strain on enhancement of ferroelectric polarization was studied. The size dependence and the role of interfaces in the observed enhancements of the dielectric behaviors were highlighted. The tunability of about 55% was achieved in these systems and was higher than any of the single polycrystalline thin film of the constituent materials reported till date. The enhanced dielectric properties were thus discussed in terms of the interfacial strain driven polar region due to high lattice mismatch and electrostatic coupling due to polarization mismatch between individual layers. Chapter 6 deals with the dielectric response, impedance spectroscopy and the DC leakage characteristics of the superlattice structures. All the heterostructures fabricated, exhibited low frequency dispersion, similar to that of the Jonscher’s universal type of relaxation behavior. The anomalous dispersion was observed in the imaginary dielectric constant at high frequencies. A Debye type relaxation behavior was observed in the impedance analysis at low temperatures, whereas, a departure from ideal ‘Debye’ type was noticed as the temperature was increased. The leakage currents of all the heterostructures were found to be a few orders less than the homogeneous single layer thin films. A space charge limited conduction was observed in al the superlattice structures fabricated. Chapter 7 summarizes the present study and discusses about the future work that could give more insight into the understanding of the ferroelectric perovskite heterostructures.