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Thermoelectricity transforms temperature gradients across thermoelectric material into an external voltage through a phenomenon known as the Seebeck effect. This property has resulted in niche applications such as solid-state cooling for electronic and optoelectronic devices which exclude the need for a coolant or any moving parts and long-lasting, maintenance-free radioisotope thermoelectric generators used for deep-space exploration. However, the high price and low efficiency of thermoelectric generators have prompted scientists to search for new materials and/or methods to improve the efficiency of the already existing ones. Thermoelectric efficiency is governed by the dimensionless figure of merit ????, which depends on the electrical conductivity, thermal conductivity and Seebeck coefficient value of the material and has rarely surpassed unity. In order to address these issues, research conducted on early transition metal nitrides spearheaded by cubic scandium nitride (ScN) thin films showed promising results with high power factors close to 3000 ?Wm?1K?2 at 500 °C. These results are the main motivation behind my thesis where the conducted research is separated into two different routes: • the synthesis and characterization of chromium nitride thin films and its alloys • the study of hypothetical ternary nitrides equivalent to scandium nitride Rock-salt cubic chromium nitride (CrN) deposited in the form of thin films by reactive magnetron sputtering was chosen for its large Seebeck coefficient of approximately -200 ?V/K and low thermal conductivity between 2 and 4 Wm?1K?1. The results show that CrN in single crystal form has a low electrical resistivity below 1 m?cm, a Seebeck coefficient value of -230 ?V/K and a power factor close to 5000 ?Wm?1K?2 at room temperature. These promising results could lead to CrN based thermoelectric modules which are cheaper and more stable compared to traditional thermoelectric material such as bismuth telluride (Bi2Te3) and lead telluride (PbTe). Although cubic CrN has been shown to be a promising material for research with a large power factor, the electrical resistivity limits applications in pure form as the ???? is estimated to be slightly below 0.5. To overcome this issue, I enhanced the thermoelectric power-factor of CrN by alloying it with a conductor, Rock-salt cubic vanadium nitride (VN). VN is a suitable choice as both materials share the same crystal structure and have almost equal lattice constants. Through deposition at 720 °C, where a small amount of VN (less than 5%) and Cr2N is introduced into the film, a reduced electrical resistivity averaged around 0.8 × 10-3 ?cm, Seebeck coefficient value of 270 ?V/K and a power-factor of 9.1 × 10-3 W/mK2 is measured at room temperature, which surpasses the thermoelectric properties of Bi2Te3. Hexagonal dichromium nitride (Cr2N) nano-inclusions increase the charge carrier concentration and act as phonon scattering sites. Single crystal Cr2N was also studied separately, as it shows interesting elastic-plastic mechanical properties and high resistance to oxidation at high temperatures for long periods of time. In the second part of this thesis, hypothetical ternary nitrides equivalent to ScN are investigated for their prospective thermoelectric properties. Scandium nitride has a relatively high thermal conductivity value (close to 10 Wm?1K?1), resulting in a low ????. A hypothetical ternary equivalent to ScN may have a similar electronic band structure and large power factor, but with a lower thermal conductivity value leading to better thermoelectric properties. Thus, the elements magnesium, titanium, zirconium, and hafnium were chosen for this purpose. DFT calculations were used to simulate TiMgN2, ZrMgN2 and HfMgN2. The results show the MeMgN2 stoichiometry to be stable, with two rivaling crystal structures: trigonal NaCrS2 and monoclinic LiUN2. The calculated electronic band structure of these compounds shows a direct band-gap for the monoclinic and an indirect band-gap for the trigonal crystal structures. These findings, coupled with predicted Seebeck coefficient values, encourages actual synthesis of such materials. DFT calculations were also used to study (Zr, Mg)N and (Hf, Mg)N alloys based on the SQS model. The transition temperature between the ordered monoclinic structure of ZrMgN2 and HfMgN2 and the disordered (Zr, Mg)N and (Hf, Mg)N alloys is calculated to be approximately 800 K and 1050 K respectively. Density of State (DoS) calculations show that similar to (Ti, Mg)N, (Zr, Mg)N and (Hf, Mg)N are also semiconducting. The thermoelectric properties of both compounds are also predicted, and that in the range of a moderate change in the Fermi level, high Seebeck coefficient values at room temperature can be achieved. Finally, in order to complete the mentioned study on hypothetical ternaries, I deposited (Ti, Mg)N thin film alloys by reactive magnetron sputtering. These films, which were deposited at 400 °C, are porous and are crystallized in the rocksalt cubic structure. As-deposited films show an electrical resistivity of 150 m?cm and a Seebeck coefficient of -25 ?V/K, which shows semiconducting properties. In order to initiate a phase transformation, these films when annealed at approximately 800 °C, where nano-inclusions of a titanium/magnesium oxynitride are formed in a LiTiO2-type superstructure are identified by XRD and TEM analysis.
Nitrides are used as coatings and thin films for a wide range of applications. The study and use of nitrides in the recent decades have shifted towards ternary, quaternary or even higher order (complex) nitrides. There is an interest to use ternary and quaternary nitrides for machining and thermoelectric materials, because it gives the possibility to choose composition and thereby design the materials properties. This thesis presents research results on TiAlN and and TiAlN-based coatings that are used as hard coatings for machining and on ternary scandium nitrides that are of interest for thin films for thermoelectric applications. The high-pressure high-temperature behavior of cubic TiAlN deposited on cubic boron nitride has been experimentally studied. It has been shown that the spinodal decomposition, which means decomposition into cubic domains enriched in TiN and AlN, is delayed as a result of high pressure compared to ambient pressure. No chemical interaction between coating and substrate occurs. TiZrAlN has been theoretically and experimentally studied at high temperature. The results show that the when Zr-content is decreased and the Al-content is increased the decomposition route changes from nucleation and growth to spinodal decomposition. The microstructure evolution with temperature depends on the initial composition. In the case where the decompositon starts with only spinodal decomposition the microstructure at 1100 °C consists of domains that are larger than in the case where the decomposition occurs by nucleation and growth. ScMN2 (M=V, Nb, Ta) phases have been experimentally demonstrated for M=Nb and Ta in a few studies, but have not been much investigated. In this theseis, their crystal structure, stability, elastic properties, electronic structure and thermoelectric properties have been studied. At 0 K and 0 GPa it has been shown that these three phases are thermodynamically and elastically stable. Additionally, these are narrow-bandgap semiconductors and their thermoelectric properties can be tuned by doping. Pressure has a stabilizing effect on these structures. When pressure increases from 0-150 GPa the elastic constants and moduli increases in the range 53-317 %.
Refractory Materials, Volume 7: Transition Metal Carbides and Nitrides discusses the developments in transition metal carbide and nitride research. This volume is organized into nine chapters that emphasize the mechanical and superconducting properties of these compounds. The introductory chapters deal with the general properties, preparation techniques, characterization, crystal chemistry, phase relationships, and thermodynamics of transition metal carbides and nitrides. The following chapter highlights the mechanical properties of these compounds, such as elastic and plastic deformation, fracture, strengthening mechanisms, and hardness. The discussion then shifts to specific electrical and magnetic properties, including electrical resistivity, Hall coefficient, and magnetic susceptibility. A separate chapter is devoted to carbides and nitrides as superconductors. The concluding chapters explore certain theories that explain the mechanisms of band structure and bonding in carbides and nitrides. This volume is of great value to research workers in metallurgy, ceramics, physics, chemistry, and related fields, as well as to advanced students investigating problems concerning high temperature materials or interstitial compounds.
This book arose from a symposium titled 'Transition Metal Carbides and Nitrides: Preparation, Properties, and Reactivity' organized by Jae Sung Lee, Masatoshi Nagai and myself. The symposium was part of the 1995 Congress of Pacific Rim Chemical Societies, held in Honolulu, Hawaii between December 17-22, 1995. The meeting was the first major conference to exclusively address the theme of metal carbides and nitrides, and brought together many of the major researchers in the field. Over 50 scientists and engineers reported their latest findings in five sessions of presentations and discussions. The book closely follows the topics covered in the conference: Theory of bonding Structure and composition Catalytic properties Physical properties New methods of preparation Spectroscopy and microscopy The book is unique in its coverage. It provides a general introduction to the properties and nature of the materials, but also covers their latest applications in a wide variety of fields. It should thus be of interest to both experts and nonexperts in the fields of material science, solid-state chemistry, physics, ceramics engineering, and catalysis. The first chapter gives an overview, and many of the chapters provide summaries of advanced topics. All contributions were peer-reviewed.
This book will provide readers with deep insight into the intriguing science of thermoelectric thin films. It serves as a fundamental information source on the techniques and methodologies involved in thermoelectric thin film growth, characterization and device processing. This book involves widespread contributions on several categories of thermoelectric thin films: oxides, chalcogenides, iodates, nitrides and polymers. This will serve as an invaluable resource for experts to consolidate their knowledge and will provide insight and inspiration to beginners wishing to learn about thermoelectric thin films. Provides a single-source reference on a wide spectrum of topics related to thermoelectric thin films, from organic chemistry to devices, from physical chemistry to applied physics, from synthesis to device implementation; Covers several categories of thermoelectric thin films based on different material approaches such as oxides, chalcogenides, iodates, nitrides and polymers; Discusses synthesis, characterization, and device processing of thermoelectric thin films, as well as the nanoengineering approach to tailor the properties of the used materials at the nanoscale level.
The field of coatings and thin-film technologies is rapidly advancing to keep up with new uses for semiconductor, optical, tribological, thermoelectric, solar, security, and smart sensing applications, among others. In this sense, thin-film coatings and structures are increasingly sophisticated with more specific properties, new geometries, large areas, the use of heterogeneous materials and flexible and rigid coating substrates to produce thin-film structures with improved performance and properties in response to new challenges that the industry presents. This book aims to provide the reader with a complete overview of the current state of applications and developments in thin-film technology, discussing applications, health and safety in thin films, and presenting reviews and experimental results of recognized experts in the area of coatings and thin-film technologies.
This book describes the rapidly expanding field of two-dimensional (2D) transition metal carbides and nitrides (MXenes). It covers fundamental knowledge on synthesis, structure, and properties of these new materials, and a description of their processing, scale-up and emerging applications. The ways in which the quickly expanding family of MXenes can outperform other novel nanomaterials in a variety of applications, spanning from energy storage and conversion to electronics; from water science to transportation; and in defense and medical applications, are discussed in detail.
MXene Reinforced Polymer Composites This volume is the first book to comprehensively explore the various fabrication and processing strategies for MXene-reinforced polymer composites including detailed characterizations and their numerous applications. The book systematically provides a critical discussion on the synthesis and processing methods, structure, properties, characterizations, surface chemistry, and functionalization strategies of MXenes and their utilization as efficient nanofiller into various polymer matrices to form high-performance polymer composites. The book provides a deep insight into the recent state-of-the-art progress in MXene-reinforced polymer composites, discussing several critical issues and providing suggestions for future work. The key features of this book are: Providing fundamental information and a clear understanding of the synthesis, processing, compositions, structure, and physicochemical properties of MXenes; Presenting a comprehensive review of several recent accomplishments and key scientific and technological challenges in developing MXene-reinforced polymer composites; Exploring various processing and fabrication methods of MXene-reinforced polymer composites; Providing deep insight into fundamental properties and various emerging applications of MXene-reinforced polymer/composites. Audience Researchers, postgraduates, and industry engineers working in materials science, polymer science, materials engineering, and nanotechnology, as well as technologists in electronic, electrical, and biomedical industries.