| 1. |
- Alkaissi, Hammoudi, 1983-
(author)
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Identification of candidate genes involved in Mercury Toxicokinetics and Mercury Induced Autoimmunity
- 2018
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Doctoral thesis (other academic/artistic)abstract
- BACKGROUND: Autoimmune diseases require the involvement and activation of immune cells and occur when the body builds up an immune response against its own tissues. This process takes place due to the inability to distinguish self-antigen from foreign antigen. Systemic autoimmunity represents an important cause of morbidity and mortality in humans. The mechanisms triggering autoimmune responses are complex and involve a network of genetic factors. Genome wide association study (GWAS) is a powerful method, used to identify genetic risk factors in numerous diseases, such as systemic autoimmune diseases. The goal of GWAS is to identify these genetic risk factors in order to make predictions about who is at risk and investigate the biological process of disease susceptibility. There are several valuable mouse models to investigate the underlying mechanisms causing systemic autoimmune diseases in which mercury induced autoimmunity (HgIA) is a well- established and relevant model. HgIA in mice includes development of autoantibodies, immune complex glomerulonephritis, lymphocyte proliferation, hypergammaglobulinemia and polyclonal B cell activation. In humans, mercury exposure accumulates with considerable concentrations in kidney, liver, and brain. Toxicokinetics of Hg has been studied extensively but the key for inter-individual variation in humans are largely unclear. Differences in accumulation of renal Hg between inbred mouse strains suggest a genetic inter-strain variation regulating retention or/and excretion of Hg.OBJECTIVES: To find loci and candidate genes associated with phenotypes involved in the development of autoimmunity and find candidate genes involved in the regulation of renal Hg excretion.METHODS: MHC II (H-2s) mice were paired (A.SW x B10.S) to obtain F2 offspring exposed to 2.0 or 4.0 mg Hg in drinking water for 6 weeks. Mercury induced autoimmune phenotypes were studied with immunofluorescence (anti-nucleolar antibodies (ANoA)), ELISA anti-DNP/anti-ssDNA (polyclonal B cell activation), anti-chromatin antibodies (ACA) (4.0 mg Hg), and serum IgG1 concentrations. Mercury accumulation in kidney was performed previously and data was included as phenotype. F2 mice exposed to 2.0 mg Hg were genotyped with microsatellites for genome-wide scan with Ion Pair Reverse Phase High Performance Liquid Chromatography (IP RP HPLC). F2 mice exposed to 4.0 mg Hg were genotyped with single nucleotide polymorphisms for genomewide scan with SNP&SEQ technology platform. Quantitative trait loci (QTL) was established with R/QTL. Denaturing HPLC, next generation sequencing, conserved region analysis and genetic mouse strain comparison were used for haplotyping and fine mapping on QTLs associated with Hg concentration in kidney, development of ANoA and serum IgG1 hypergammaglobulinemia. Candidate genes (Pprc1, Bank1 and Nfkb1) verified by additional QTL were further investigated by real time polymerase chain reaction. Genes involved in the intracellular signaling together with candidate genes were included for gene expression analysis.RESULTS: F2 mice exposed to 2.0 mg Hg had low or no development of autoantibodies and showed no significant difference in polyclonal B cell activation in the B10.S and F2 strains. F2 mice exposed to 4.0 mg Hg developed autoantibodies and significantly increased IgG1 concentration and polyclonal B cell activation (anti-DNP). QTL analysis showed a logarithm of odds ratio (LOD) score between 2.9 – 4.36 on all serological phenotypes exposed to 4.0 mg Hg, and a LOD score of 5.78 on renal Hg concentration. Haplotyping and fine mapping associated the development of ANoA with Bank1 (B-cell scaffold protein with ankyrin repeats 1) and Nfkb1 (nuclear factor kappa B subunit 1). The serum IgG1 concentration was associated with a locus on chromosome 3, in which Rxfp4 (Relaxin Family Peptide/INSL5 Receptor 4) is a potential candidate gene. The renal Hg concentration was associated with Pprc1 (Peroxisome Proliferator-Activated Receptor Gamma, Co-activator-Related). Gene expression analysis revealed that the more susceptible A.SW strain expresses significantly higher levels of Nfkb1, Il6 and Tnf than the less susceptible B10.S strain. The A.SW strain expresses significantly lower levels of Pprc1 and cascade proteins than the B10.S strain. Development of ACA was associated with chromosomes 3, 6, 7 and 16 (LOD 3.1, 3.2, 3.4 and 6.8 respectively). Polyclonal B cell activation was associated with chromosome 2 with a LOD score of 2.9.CONCLUSIONS: By implementing a GWAS on HgIA in mice, several QTLs were discovered to be associated with the development of autoantibodies, polyclonal B cell activation and hypergammaglobulinemia. This thesis plausibly supports Bank1 and Nfkb1 as key regulators for ANoA development and HgIA seems to be initiated by B cells rather than T cells. GWAS on renal mercury excretion plausibly supports Pprc1 as key regulator and it seems that this gene has a protective role against Hg.
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| 2. |
- Fashandi, Hossein, 1984-
(author)
-
Novel Layered and 2D Materials for Functionality Enhancement of Contacts and Gas Sensors
- 2016
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Doctoral thesis (other academic/artistic)abstract
- Chemical gas sensors are widely-used electronic devices for detecting or measuring the density levels of desired gas species. In this study, materials with established or potential applications for gas sensors are treated. For the case of high-temperature applications (≈ 600 °C), semiconductor-based gas sensors suffer from rapid oxidation of the metallic ohmic contacts, the same cause-of-failure as for the general case of high-temperature semiconductor electronics. 4H-SiC is an ideal semiconductor for high-temperature applications. Ti3SiC2 is a known ohmic contact to 4H-SiC with the known two-step synthesis process of post-annealing of pre-deposited Ti/Al multilayers or sputter-deposition of Ti3SiC2 films at > 900 °C. Here, sputter-deposition of Ti on 4H-SiC at > 900 °C is presented as a novel single-step method for the synthesis of Ti3SiC2 ohmic contacts, based on a concurrent reaction between sputter-deposited Ti and 4HSiC. Ti3SiC2, similar to any other known ohmic contact, degrade rapidly in high-temperature oxidizing ambient. To try to overcome this obstacle, noble metal diffusion into Ti3SiC2 has been s studied with the goal to retain ohmic properties of Ti3SiC2 and harnessing oxidation resistivity of noble metals. A novel exchange intercalation between Ti3SiC2 and Au is discovered which results in the almost complete exchange of Si with Au giving rise to novel Ti3AuC2 and Ti3Au2C2. Ti3IrC2 is also synthesized through exchange intercalation of Ir into Ti3Au2C2. All the aforementioned phases showed ohmic properties to 4H-SiC. This technique is also studied based on Ti2AlC and Ti3AlC2 resulting in the synthesis of novel Ti2Au2C and Ti3Au2C2, respectively. Using Ti3AuC2 and an Au/IrOx capping layer, an ohmic contact was manufactured, which maintained ohmic properties and showed no structural defects after 1000 h of aging at 600 °C air.Ti3SiC2 is a member of a large family of materials known as Mn+1AXn phases. While exchange reactions of Si (or Al) planes in Ti3SiC2 (Ti2AlC and Ti3AlC2) is presented here, a world-wide research already exists on chemical removal of the same atomic planes from different Mn+1AXn phases and the synthesis of Mn+1Xn sheets known as MXenes. I performed a theoretical study regarding simulation of electronic and structural properties of more than120 different possible MXene phases. The results show that some MXene phases, when terminated by particular gas species, turn into Dirac materials. That is, they possess massless Dirac fermions with different properties compared to graphene such as higher number of Dirac points at the Fermi level, giant spin orbit splitting, and preserved 2D-type electronic properties by extending the dimensionality. The general substantial change of the electronic properties of MXenes under different gas adsorption configurations stands out and can thus be harnessed for sensing applications.Growth of monolayer iron oxide on porous Pt sensing layers is another novel approach used in this study for applying the unique properties of 2D materials for gas sensors. A low temperature shift in CO oxidation characteristics is presented. The approach is similar to that previously reported using bulk single crystal Pt substrate, the latter being an unrealistic model for sensors and catalysts. Monolayer-coated Pt sensing layers were fabricated as the metal component of a metal oxide semiconductor (MOS) capacitor device, whereby the electrical response of the MOS device could be used to map out the catalytic properties of the sensing layer. The monolayer-coated Pt surface showed to be stable with retained improved catalytic properties for > 200 h. The MOS device measurements are here utilized as a handy method for in-situ monitoring of the surface chemical properties of the monolayer-coated Pt and the approach is highly functional for use and characterization of monolayer coatings of widely used sensingor catalytic layers.
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| 3. |
- Halim, Joseph, 1985-
(author)
-
Synthesis and transport properties of 2D transition metal carbides (MXenes)
- 2018
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Doctoral thesis (other academic/artistic)abstract
- Since the isolation and characterization of graphene, there has been a growing interest in 2D materials owing to their unique properties compared to their 3D counterparts. Recently, a family of 2D materials of early transition metal carbides and nitrides, labelled MXenes, has been discovered (Ti2CTz, Ti3C2Tz, Mo2TiC2Tz, Ti3CNTz, Ta4C3Tz, Ti4N3Tz among many others), where T stands for surface-terminating groups (O, OH, and F). MXenes are mostly produced by selectively etching A layers (where A stands for group A elements, mostly groups 13 and 14) from the MAX phases. The latter are a family of layered ternary carbides and/or nitrides and have a general formula of Mn+1AXn (n = 1-3), where M is a transition metal and X is carbon and/or nitrogen. The produced MXenes have a conductive carbide core and a non-conductive O-, OH- and/or F-terminated surface, which allows them to work as electrodes for energy storage applications, such as Li-ion batteries and supercapacitors.Prior to this work, MXenes were produced in the form of flakes of lateral dimension of about 1 to 2 microns; such dimensions and form are not suitable for electronic characterization and applications. I have synthesized various MXenes (Ti3C2Tz, Ti2CTz and Nb2CTz) as epitaxial thin films, a more suitable form for electronic and photonic applications. These films were produced by HF, NH4HF2 or LiF + HCl etching of magnetron sputtered epitaxial Ti3AlC2, Ti2AlC, and Nb2AlC thin films. For transport properties of the Ti-based MXenes, Ti2CTz and Ti3C2Tz, changing n from 1 to 2 resulted in an increase in conductivity but had no effect on the transport mechanism (i.e. both Ti3C2Tx and Ti2CTx were metallic). In order to examine whether the electronic properties of MXenes differ when going from a few layers to a single flake, similar to graphene, the electrical characterization of a single Ti3C2Tz flake with a lateral size of about 10 μm was performed. These measurements, the first for MXene, demonstrated its metallic nature, along with determining the nature of the charge carriers and their mobility. This indicates that Ti3C2Tz is inherently of 2D nature independent of the number of stacked layers, unlike graphene, where the electronic properties change based on the number of stacked layers.Changing the transition metal from Ti to Nb, viz. comparing Ti2CTz and Nb2CTz thin films, the electronic properties and electronic conduction mechanism differ. Ti2CTz showed metallic-like behavior (resistivity increases with increasing temperature) unlike Nb2CTz where the conduction occurs via variable range hopping mechanism (VRH) - where resistivity decreases with increasing temperature.Furthermore, these studies show the synthesis of pure Mo2CTz in the form of single flakes and freestanding films made by filtering Mo2CTz colloidal suspensions. Electronic characterization of free-standing films made from delaminated Mo2CTz flakes was investigated, showing that a VRH mechanism prevails at low temperatures (7 to ≈ 60 K). Upon vacuum annealing, the room temperature, RT, conductivity of Mo2CTx increased by two orders of magnitude. The conduction mechanism was concluded to be VRH most likely dominated by hopping within each flake.Other Mo-based MXenes, Mo2TiC2Tz and Mo2Ti2C3Tz, showed VRH mechanism at low temperature. However, at higher temperatures up to RT, the transport mechanism was not clearly understood. Therefore, a part of this thesis was dedicated to further investigating the transport properties of Mo-based MXenes. This includes Mo2CTz, out-of-plane ordered Mo2TiC2Tz and Mo2Ti2C3Tz, and vacancy ordered Mo1.33CTz. Magneto-transport of free-standing thin films of the Mo-based MXenes were studied, showing that all Mo-based MXenes have two transport regimes: a VRH mechanism at lower temperatures and a thermally activated process at higher temperatures. All Mo-based MXenes except Mo1.33CTz show that the electrical transport is dominated by inter-flake transfer. As for Mo1.33CTz, the primary electrical transport mechanism is more likely to be intra-flake.The synthesis of vacancy ordered MXenes (Mo1.33CTz and W1.33CTz) raised the question of possible introduction of vacancies in all MXenes. Vacancy ordered MXenes are produced by selective etching of Al and (Sc or Y) atoms from the parent 3D MAX phases, such as (Mo2/3Sc1/3)2AlC, with in-plane chemical ordering of Mo and Sc. However, not all quaternary parent MAX phases form the in-plane chemical ordering of the two M metals; thus the synthesis of the vacancy-ordered MXenes is restricted to a very limited number of MAX phases. I present a new method to obtain MXene flakes with disordered vacancies that may be generalized to all quaternary MAX phases. As proof of concept, I chose Nb-C MXene, as this 2D material has shown promise in several applications, including energy storage, photothermal cell ablation and photocatalysts for hydrogen evolution. Starting from synthetizing (Nb2/3Sc1/3)2AlC quaternary solid solution and etching both the Sc and Al atoms resulted in Nb1.33C material with a large number of vacancies and vacancy clusters. This method may be applicable to other quaternary or higher MAX phases wherein one of the transition metals is more reactive than the other, and it could be of vital importance in applications such as catalysis and energy storage.
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| 4. |
- Lai, Chung-Chuan
(author)
-
Phase Formation of Nanolaminated Transition Metal Carbide Thin Films
- 2017
-
Doctoral thesis (other academic/artistic)abstract
- Research on inherently nanolaminated transition metal carbides is inspired by their unique properties combining metals and ceramics, such as higher damage tolerance, better machinability and lower brittleness compared to the binary counterparts, yet retaining the metallic conductivity. The interesting properties are related to their laminated structure, composed of transition-metalcarbide layers interleaved by non-transition-metal (carbide) layers. These materials in thin-film form are particularly interesting for potential applications such as protective coatings and electrical contacts. The goal of this work is to explore nanolaminated transition metal carbides from the aspects of phase formation and crystal growth during thin-film synthesis. This was realized by studying phases in select material systems synthesized from two major approaches, namely, fromdirect-deposition and post-deposition treatment.The first approach was used in studies on the Mo-Ga-C and Zr-Al-C systems. In the former system, intriguing properties have been predicted for the 3D phases and their 2D derivatives (socalled MXenes), while in the latter system, the phases are interesting for nuclear applications. In this work, the discovery of a new Mo-based nanolaminated ternary carbide, Mo2Ga2C, is evidenced from thin-film and bulk processes. Its structure was determined using theoretical and experimental techniques, showing that Mo2Ga2C has Ga double-layers in simple hexagonal stacking between adjacent Mo2C layers, and therefore is structurally very similar to Mo2GaC, except for the additional Ga layers. For the Zr-Al-C system, the optimization of phase composition and structure of Zr2Al3C4 in a thin-film deposition process was studied by evaluating the effect of deposition parameters. I concluded that the formation of Zr2Al3C4 is favored with a plasma flux overstoichiometric in Al, and with a minimum lattice-mismatch to the substrates. Consequently, epitaxial Zr2Al3C4 thin film of high quality were deposited on 4H-SiC(001) substrates at 800 °C.With the approach of post-deposition treatment, the studies were focused on a new method of thermally-induced selective substitution reaction of Au for the non-transition-metal layers in nanolaminated carbides. Here, the reaction mechanism has been explored in Al-containing (Ti2AlCand Ti3AlC2) and Ga-containing (Mo2GaC and Mo2Ga2C) phases. The Al and Ga in these phases were selectively replaced by Au while the carbide layers remained intact, resulting in the formation of new layered phases, Ti2Au2C, Ti3Au2C2, Mo2AuC, and Mo2(Au1-xGax)2C, respectively. The substitution reaction was explained by fast outward diffusion of the Al or Ga being attracted to the surface Au, in combination with back-filling of Au, which is chemically inert to the carbide layers,to the vacancies.The substitution reaction was further applied to Ga-containing nanolaminated carbides, (Cr0.5Mn0.5)2GaC and Mo2GaC, motivated by development of novel magnetic nanolaminates. The former experiment resulted in the formation of (Cr0.5Mn0.5)2AuC, where the retained (Cr0.5Mn0.5)2C layers allowed a comparative study on the magnetic properties under the exchange of Ga for Au. After Au substitution, reduction in the Curie temperature and the saturation magnetization were observed, showing a weakened magnetic exchange interaction of the magnetic (Cr0.5Mn0.5)2 Clayers across the Au. In the Mo2GaC case, an Fe-containing MAX phase, Mo2AC with 50 at.% of Fe on the A site, was synthesized through selective substitution of Au-Fe alloy for the Ga layers, showing the first direct evidence for Fe in the MAX-phase structure. The substitution of Fe did not take place on another Mo2GaC sample tested for Fe exchange only, indicating the essential role of Au in catalyzing the Fe-substitution reaction.The knowledge gained from this thesis work contributes to improved approaches for attaining thin films of nanolaminated transition metal carbides with desired phase composition and crystal quality. The reports on the new nanolaminated phases through exchange interactions are likely to expand the family of nanolaminated carbides and advance their properties, and trigger more studies on related (quasi-) 2D materials.
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| 5. |
- Ding, Haoming, et al.
(author)
-
Synthesis of MAX phases Nb2CuC and Ti2(Al0.1Cu0.9)N by A-site replacement reaction in molten salts
- 2019
-
In: Materials Research Letters. - : Taylor & Francis. - 2166-3831. ; 7:12, s. 510-516
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Journal article (peer-reviewed)abstract
- New MAX phases Ti2(AlxCu1−x)N and Nb2CuC were synthesized by A-site replacement by reacting Ti2AlN and Nb2AlC, respectively, with CuCl2 or CuI molten salt. X-ray diffraction, scanning electron microscopy, and atomically resolved scanning transmission electron microscopy showed complete A-site replacement in Nb2AlC, which lead to the formation of Nb2CuC. However, the replacement of Al in Ti2AlN phase was only close to complete at Ti2(Al0.1Cu0.9)N. Density-functional theory calculations corroborated the structural stability of Nb2CuC and Ti2CuN phases. Moreover, the calculated cleavage energy in these Cu-containing MAX phases are weaker than in their Al-containing counterparts.The preparation of MAX phases Nb2CuC and Ti2(Al0.1Cu0.9)N were realized by A-site replacement in Ti2AlN and Nb2AlN, respectively.
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| 6. |
- Kerdsongpanya, Sit, 1985-
(author)
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Design of Transition-Metal Nitride Thin Films for Thermoelectrics
- 2015
-
Doctoral thesis (other academic/artistic)abstract
- Thermoelectric devices are one of the promising energy harvesting technologies, because of their ability to convert heat (temperature gradient) to electricity by the Seebeck effect. Furthermore, thermoelectric devices can be used for cooling or heating by the inverse effect (Peltier effect). Since this conversion process is clean, with no emission of greenhouse gases during the process, this technology is attractive for recovering waste heat in automobiles or industries into usable electricity. However, the conversion efficiency of such devices is rather low due to fundamental materials limitations manifested through the thermoelectric figure of merit (ZT). Thus, there is high demand on finding materials with high ZT or strategies to improve ZT of materials.In this thesis, I discuss the basics of thermoelectrics and how to improve ZT of materials, including present-day strategies. Based on these ideas, I propose a new class of materials for thermoelectric applications: transition-metal nitrides, mainly ScN, CrN and their solid solutions. Here, I employed both experimental and theoretical methods to synthesize and study their thermoelectric properties. My study envisages ways for improving the thermoelectric figure of merit of ScN and possible new materials for thermoelectric applications.The results of my studies show that ScN is a promising thermoelectric material since it exhibits high thermoelectric power factor 2.5x10-3 Wm-1K-2 at 800 K, due to low metallic-like electrical resistivity while retained relatively large Seebeck coefficient. My studies on thermal conductivity of ScN also suggest a possibility to control thermal conductivity by tailoring the microstructure of ScN thin films. Furthermore, my theoretical studies on effects of impurities and stoichiometry on the electronic structure of ScN suggest the possibly to improve ScN ZT by stoichiometry tuning and doping. For CrN and Cr1-xScxN solid solution thin films, the results show that the power factor of CrN (8x10-4 Wm-1K-2 at 770 K) can be retained for the solid solution Cr0.92Sc0.08N. Finally, density functional theory was used to enable a systematic predictionbased strategy for optimizing ScN thermoelectric properties via phase stability of solid solutions. Sc1-xGdxN and Sc1-xLuxN are stabilized as disordered solid solutions, while in the Sc-Nb-N and Sc-Ta-N systems, the inherently layered ternary structures ScNbN2 and ScTaN2 are stable.
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| 7. |
- Serban, Alexandra, 1988-
(author)
-
Magnetron Sputter Epitaxy of Group III-Nitride Semiconductor Nanorods
- 2017
-
Licentiate thesis (other academic/artistic)abstract
- The III-nitride semiconductors family includes gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN), and related ternary and quaternary alloys. The research interest on this group of materials is sparked by the direct bandgaps, and excellent physical and chemical properties. Moreover, the ternary alloys (InGaN, InAlN and AlGaN) present the advantage of bandgap tuning, giving access to the whole visible spectrum, from near infrared into deep ultraviolet wavelengths. The intrinsic properties of III-nitride materials can be combined with characteristical features of nanodimension and geometry in nanorod structures. Moreover, nanorods offer the advantage of avoiding problems arising from the lack of native substrates, like lattice and thermal expansion, film – substrate mismatch.The growth and characterization of group III-nitride semiconductos nanorods, namely InAlN and GaN nanorods, is presented in this thesis. All the nanostructures were grown by employing direct-current reactive magnetron sputter epitaxy. InxAl1−xN self-assembled, core-shell nanorods on Si(111) substrates were demonstrated. A comprehensive study of temperature effect upon the morphology and composition of the nanorods was realized. The radial nanorod heterostructure consists of In-rich cores surrounded by Al-rich shells with different thicknesses. The spontaneous formation of core-shell nanorods is suggested to originate from phase separation due to spinodal decomposition. As the growth temperature increase, In desorption is favored, resulting in thicker Al-rich shells and larger nanorod diameters.Both self-assembled and selective-area grown GaN nanorods are presented. Self-assembled growth of GaN nanorods on cost-effective substrates offers a cheaper alternative and simplifies device processing. Successful growth of high- quality GaN (exhibiting strong bandedge emission and high crystalline quality) on conductive templates/substrates such as Si, SiC, TiN/Si, ZrB2/Si, ZrB2/SiC, Mo, and Ti is supported by the possibility to be used as electrodes when integrated in optoelectronic devices.The self-assembled growth leads to mainly random nucleation, resulting in nanorods with large varieties of diameters, heights and densities within a single growth run. This translates into non-uniform properties and complicates device processing. These problems can be circumvented by employing selective-area growth. Pre-patterned substrates by nano-sphere lithography resulted in GaN nanorods with controlled length, diameter, shape, and density. Well-faceted c-axis oriented GaN nanorods were grown directly onto the native SiOx layer inside nano-opening areas, exhibiting strong bandedge emission at room- temperature and single-mode lasing. Our studies on the growth mechanism revealed a different growth behavior when compared with selective-area grown GaN nanorods by MBE and MOCVD. The time-dependent growth series helped define a comprehensive growth mechanism from the initial thin wetting layer formed inside the openings, to the well-defined, uniform, hexagonal NRs resulted from the coalescence of multiple initial nuclei.
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| 8. |
- Edström, Daniel, 1986-, et al.
(author)
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Mechanical properties of VMoNO as a function of oxygen concentration : Toward development of hard and tough refractory oxynitrides
- 2019
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In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Institute of Physics (AIP). - 0734-2101 .- 1520-8559. ; 37:6
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Journal article (peer-reviewed)abstract
- Improved toughness is a central goal in the development of wear-resistant refractory ceramic coatings. Extensive theoretical and experimental research has revealed that NaCl-structure VMoN alloys exhibit surprisingly high ductility combined with high hardness and toughness. However, during operation, protective coatings inevitably oxidize, a problem that may compromise material properties and performance. Here, the authors explore the role of oxidation in altering VMoN properties. Density functional theory and theoretical intrinsic hardness models are used to investigate the mechanical behavior of cubic V0.5Mo0.5N1-xOx solid solutions as a function of the oxygen concentration x. Elastic constant and intrinsic hardness calculations show that oxidation does not degrade the mechanical properties of V0.5Mo0.5N. Electronic structure analyses indicate that the presence of oxygen reduces the covalent bond character, which slightly lowers the alloy strength and intrinsic hardness. Nevertheless, the character of metallic d-d states, which are crucial for allowing plastic deformation and enhancing toughness, remains unaffected. Overall, the authors' results suggest that VMoNO oxynitrides, with oxygen concentrations as high as 50%, possess high intrinsic hardness, while still being ductile. Published by the AVS.
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| 9. |
- Landälv, Ludvig, 1982-, et al.
(author)
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Influence of Si doping and O-2 flow on arc-deposited (Al,Cr)(2)O-3 coatings
- 2019
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In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : A V S AMER INST PHYSICS. - 0734-2101 .- 1520-8559. ; 37:6
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Journal article (peer-reviewed)abstract
- (Al,Cr)(2)O-3 coatings with Al/( Al + Cr) = 0.5 or Al = 70 at. %, doped with 0, 5, or 10 at. % Si, were deposited on hard metal and Si(100) substrates to elucidate the influence of Si on the resulting coatings. The chemical analysis of the coatings showed between 3.3 and 7.4 at. % metal fraction Si incorporated into all studied coatings depending on cathode Si composition. The incorporated Si content does not change significantly with different oxygen flows covering a wide range of deposition conditions from low to high O-2 flow during growth. The addition of Si promotes the metastable B1-like cubic structure over the thermodynamically stable corundum structure. The hardness determined by nanoindentation of the as-deposited coatings is slightly reduced upon Si incorporation as well as upon increased Al content. Si is found enriched in droplets but can also be found at a lower content, evenly spread, without visible segregation at the similar to 5 nm scale, in the actual oxide coating. The positive effect of improved cathode erosion upon Si incorporation has to be balanced against the promotion of the metastable B1-like structure, having lower room temperature hardness and inferior thermal stability compared to the corundum structure. Published by the AVS.
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| 10. |
- Landälv, Ludvig, 1982-, et al.
(author)
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Phase composition and transformations in magnetron-sputtered (Al,V)2O3 coatings
- 2019
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In: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 688
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Journal article (peer-reviewed)abstract
- Coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited by pulsed DC reactive sputter deposition on Si(100) at a temperature of 550 °C. XRD showed three different crystal structures depending on V-metal fraction in the coating: α-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, 63–42 at.% V. At lower V-content, 18 and 7 at.%, a gamma-alumina-like solid solution was observed, shifted to larger d-spacing compared to pure γ-Al2O3. The microstructure changes from large columnar faceted grains for α-V2O3 to smaller equiaxed grains when lowering the vanadium content towards pure γ-Al2O3. Annealing in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 °C for 42 at.% V and 700 °C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure γ-Al2O3-coating, which transformed to α-Al2O3 after annealing to 1100 °C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The latter decreased with increasing V-content, larger than 7 at.% V metal fraction. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings.
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| 11. |
- Landälv, Ludvig, 1982-, et al.
(author)
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Phase evolution of radio frequency magnetron sputtered Cr-rich (Cr,Zr)(2)O-3 coatings studied by in situ synchrotron X-ray diffraction during annealing in air or vacuum
- 2019
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In: Journal of Materials Research. - : CAMBRIDGE UNIV PRESS. - 0884-2914 .- 2044-5326. ; 34:22, s. 3735-3746
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Journal article (peer-reviewed)abstract
- The phase evolution of reactive radio frequency (RF) magnetron sputtered Cr0.28Zr0.10O0.61 coatings has been studied by in situ synchrotron X-ray diffraction during annealing under air atmosphere and vacuum. The annealing in vacuum shows t-ZrO2 formation starting at similar to 750-800 degrees C, followed by decomposition of the alpha-Cr2O3 structure in conjunction with bcc-Cr formation, starting at similar to 950 degrees C. The resulting coating after annealing to 1140 degrees C is a mixture of t-ZrO2, m-ZrO2, and bcc-Cr. The air-annealed sample shows t-ZrO2 formation starting at similar to 750 degrees C. The resulting coating after annealing to 975 degrees C is a mixture of t-ZrO2 and alpha-Cr2O3 (with dissolved Zr). The microstructure coarsened slightly during annealing, but the mechanical properties are maintained, with no detectable bcc-Cr formation. A larger t-ZrO2 fraction compared with alpha-Cr2O3 is observed in the vacuum-annealed coating compared with the air-annealed coating at 975 degrees C. The results indicate that the studied pseudo-binary oxide is more stable in air atmosphere than in vacuum.
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| 12. |
- Landälv, Ludvig, 1982-, et al.
(author)
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Structural evolution in reactive RF magnetron sputtered (Cr,Zr)2O3 coatings during annealing
- 2017
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In: Acta Materialia. - : PERGAMON-ELSEVIER SCIENCE LTD. - 1359-6454 .- 1873-2453. ; 131, s. 543-552
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Journal article (peer-reviewed)abstract
- Reactive RF-magnetron sputtering is used to grow Cr0.28Zr0.10O0.61 coatings at 500 degrees C. Coatings are annealed at 750 degrees C, 810 degrees C, and 870 degrees C. The microstructure evolution of the pseudobinary oxide compound is characterized through high resolution state of the art HRSTEM and HREDX-maps, revealing the segregation of Cr and Zr on the nm scale. The as-deposited coating comprises cc-(Cr,Zr)(2)O-3 solid solution with a Zr-rich (Zr,Cr)O-x. amorphous phase. After annealing to 750 degrees C tetragonal ZrO2 nucleates and grows from the amorphous phase. The ZrO2 phase is stabilized in its tetragonal structure at these fairly low annealing temperatures, possibly due to the small grain size (below 30 nm). Correlated with the nucleation and growth of the tetragonal-ZrO2 phase is an increase in hardness, with a maximum hardness after annealing to 750 degrees C, followed by a decrease in hardness upon coarsening, bcc metallic Cr phase formation and loss of oxygen, during annealing to 870 degrees C. The observed phase segregation opens up future design routes for pseudobinary oxides with tunable microstructural and mechanical properties. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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| 13. |
- Landälv, Ludvig, 1982-
(author)
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Thin Film and Plasma Characterization of PVD Oxides
- 2017
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Licentiate thesis (other academic/artistic)abstract
- The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite(WC-Co) coated with different combinations of carbide, nitride and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings are especially desired because of their possible high hot hardness, chemical inertness with respect to the workpiece, and their low friction.This thesis deals with process and coating characterization of new oxide coatings deposited by physical vapor deposition (PVD) techniques, focusing on the Cr-Zr-O and Al-Cr-Si-O systems.The thermal stability of α-Cr0.28Zr0.10O0.61 deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was investigated after annealing up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudo-binary oxide system also opens up design routes for pseudo-binary oxides with tunable microstructural and mechanical properties.The inherent difficulties of depositing insulating oxide films with PVD, demanding a closed circuit, makes the investigation of process stability an important part of this research. In this context, we investigated the influence of adding small amount of Si in Al-Cr cathode on plasma characteristics ,process parameters, and coating properties. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating.This work shows small improvements in cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at % Si in the Al70Cr30-cathode. This also led to fewer droplets at low cathode current and intermediate O2 flow. A larger positive effect on cathode erosion was observed with respect to cleaning the cathode from oxide contamination by increasing cathode current with 50%. However, higher cathode current also resulted in increased amount of droplets in the coating which is undesirable. Through plasma analysis the presence of volatile SiO species could be confirmed but the loss of Si through volatile SiO species was negligible, since the coating composition matched the cathode composition. The positive effect of added Si on the process stability at the cathode surface should be weighed against Si incorporation in the coating. This incorporation may or may not be beneficial for the final application since literature states that Si promotes the metastable γ-phase over the thermodynamically stable α-phase of pure Al2O3, contrary to the effect of Cr, which stabilizes the α-phase.
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| 14. |
- Magnuson, Martin, 1965-, et al.
(author)
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Compositional dependence of epitaxial Tin+1SiCn MAX-phase thin films grown from a Ti3SiC2 compound target
- 2019
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In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Institute of Physics (AIP). - 0734-2101 .- 1520-8559. ; 37:2
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Journal article (peer-reviewed)abstract
- The authors investigate sputtering of a Ti3SiC2 compound target at temperatures ranging from RT (no applied external heating) to 970 °C as well as the influence of the sputtering power at 850 °C for the deposition of Ti3SiC2 films on Al2O3(0001) substrates. Elemental composition obtained from time-of-flight energy elastic recoil detection analysis shows an excess of carbon in all films, which is explained by differences in the angular distribution between C, Si, and Ti, where C scatters the least during sputtering. The oxygen content is 2.6 at. % in the film deposited at RT and decreases with increasing deposition temperature, showing that higher temperatures favor high purity films. Chemical bonding analysis by x-ray photoelectron spectroscopy shows C–Ti and Si–C bonding in the Ti3SiC2 films and Si–Si bonding in the Ti3SiC2 compound target. X-ray diffraction reveals that the phases Ti3SiC2, Ti4SiC3, and Ti7Si2C5 can be deposited from a Ti3SiC2 compound target at substrate temperatures above 850 °C and with the growth of TiC and the Nowotny phase Ti5Si3Cx at lower temperatures. High-resolution scanning transmission electron microscopy shows epitaxial growth of Ti3SiC2, Ti4SiC3, and Ti7Si2C5 on TiC at 970 °C. Four-point probe resistivity measurements give values in the range ∼120 to ∼450 μΩ cm and with the lowest values obtained for films containing Ti3SiC2, Ti4SiC3, and Ti7Si2C5.
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| 15. |
- Serban, Alexandra, 1988-, et al.
(author)
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Magnetron Sputter Epitaxy of High-Quality GaN Nanorods on Functional and Cost-Effective Templates/Substrates
- 2017
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In: Energies. - Basel, Switzerland : MDPI AG. - 1996-1073. ; 10:9
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Journal article (peer-reviewed)abstract
- We demonstrate the versatility of magnetron sputter epitaxy by achieving high-quality GaN nanorods on different substrate/template combinations, specifically Si, SiC, TiN/Si, ZrB2/Si, ZrB2/SiC, Mo, and Ti. Growth temperature was optimized on Si, TiN/Si, and ZrB2/Si, resulting in increased nanorod aspect ratio with temperature. All nanorods exhibit high purity and quality, proved by the strong bandedge emission recorded with cathodoluminescence spectroscopy at room temperature as well as transmission electron microscopy. These substrates/templates are affordable compared to many conventional substrates, and the direct deposition onto them eliminates cumbersome post-processing steps in device fabrication. Thus, magnetron sputter epitaxy offers an attractive alternative for simple and affordable fabrication in optoelectronic device technology.
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| 16. |
- Serban, Elena Alexandra, 1988-
(author)
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Self-Assembled and Selective-Area Growth of Group III-Nitride Semiconductor Nanorods by Magnetron Sputter Epitaxy
- 2018
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Doctoral thesis (other academic/artistic)abstract
- The III-nitride semiconductor family includes gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN), and the related ternary and quaternary alloys. The research interest on this group of materials is sparked by the direct bandgaps, and excellent physical and chemical properties. Moreover, the ternary alloys (InGaN, InAlN and AlGaN) present the advantage of bandgap tuning, giving access to the whole visible spectrum, from near infrared into deep ultraviolet wavelengths. The intrinsic properties of III-nitride materials can be combined with characteristic features of nanodimension and geometry in nanorod structures. Moreover, nanorods offer the advantage of avoiding problems arising from the lack of native substrates with film/substrate lattice and thermal expansion mismatch.The growth and characterization of group III-nitride semiconductor nanorods, namely InAlN and GaN nanorods, is presented in this Thesis. All the nanostructures were grown by employing direct-current reactive magnetron sputter epitaxy. The results include the growth and study of both self-assembled and site-controlled grown nanorods.InxAl1−xN self-assembled, core-shell nanorods on Si(111) substrates were demonstrated. A comprehensive study of temperature effect upon the morphology and composition of the nanorods was realized. The radial nanorod heterostructure consists of In-rich cores surrounded by Al-rich shells with different thicknesses. The spontaneous formation of core-shell nanorods is suggested to originate from phase separation due to spinodal decomposition. As the growth temperature increases, In desorption is favored, resulting in thicker Al-rich shells and larger nanorod diameters. Moreover, the in-plane crystallographic relationship of the nanorods and substrate was modified from a fiber-textured to an epitaxial growth by removing the native SiOx layer from the substrate.Self-assembled growth of GaN nanorods on cost-effective substrates offers a cheaper alternative and simplifies device processing. Successful growth of high-quality GaN (exhibiting strong bandedge emission and high crystalline quality) on conductive templates/substrates such as Si, SiC, TiN/Si, ZrB2/Si, ZrB2/SiC, Mo, and Ti is supported by the possibility to be used as electrodes when integrated in optoelectronic devices. The influence of growth temperature upon the resulting size and optical properties of the nanorods was investigated. By applying a kinetic model, average diffusion length was calculated in correlation with growth temperature in order to explain the nanorods’ morphology evolution.The self-assembled growth leads to random nucleation, resulting in nanorods with large varieties of diameters, heights and densities within a single growth run. This translates into non-uniform properties and complicates device processing. These problems can be circumvented by employing selective-area growth. Pre-patterned substrates by nanosphere lithography resulted in GaN nanorods with controlled length, diameter, shape, and density. Well-faceted caxis oriented GaN nanorods were grown directly onto the native SiOx layer inside opening areas exhibiting strong bandedge emission at room-temperature and single-mode lasing. The time-dependent growth series helped define a comprehensive growth mechanism from the initial thin wetting layer formed inside the openings, to the well-defined, uniform, hexagonal nanorods resulted from the coalescence of multiple initial nuclei.Although nanosphere lithography is a fast and cheap patterning method, it does not offer the control on the size, position or density. The growth parameters were transferred onto focused ion beam lithography - patterned substrates which offers more control on the design. Focused ion beam lithography optimization included tailoring of the milling current (2-50 pA) and milling time (5-50 s). The patterning process optimisation enabled the minimization of mask and substrate damage, the key to attain uniform, welldefined, single, and straight nanorods. Destruction of the mask results in selective-area growth failure, while damage of the substrate surface promotes inclined nanorods grown into the openings, owning to random oriented nucleation. At lower growth temperatures (950 °C) nanostructures resulted from the coalescence of multiple, tilted, and irregular nanorods are observed. The tilting of the nanorods is reduced when increasing the growth temperature to 980 °C resulting in single and straight nanorods. The partial pressure of the Ar/N2 working gas was also varied for achieving selectivity and single nanorods, and study the growth behaviour. By increasing the amount of Ar in the working gas from 0 to 50%, we observe a transition of the target from a nitridized to metallic-state, affecting the sputtering conditions of the GaN nanorods. The change in the sputtering and deposition conditions influences the growth selectivity, coalescence, and growth rates. By balancing these effects, the selective growth of faceted, single nanorods was achieved.
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| 17. |
- Serban, Elena Alexandra, 1988-, et al.
(author)
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Site-controlled growth of GaN nanorod arrays by magnetron sputter epitaxy
- 2018
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In: Thin Solid Films. - : Elsevier. - 0040-6090 .- 1879-2731. ; 660, s. 950-955
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Journal article (peer-reviewed)abstract
- Catalyst-free GaN nanorod regular arrays have been realized by reactive magnetron sputter epitaxy. Two nanolithographic methods, nanosphere lithography (NSL) and focused ion beam lithography (FIBL), were applied to pattern Si substrates with TiNx masks. The growth temperature was optimized for achieving selectivity and well-faceted nanorods grown onto the NSL-patterned substrates. With increasing temperature from 875 to 985 °C, we observe different growth behaviors and associate them with selective insensitive, diffusion-dominated, and desorption-dominated zones. To further achieve site-specific and diameter control, these growth parameters were transferred onto FIBL-patterned substrates. Further investigation into the FIBL process through tailoring of milling current and time in combination with varying nanorod growth temperature, suggests that minimization of mask and substrate damage is the key to attain uniform, well-defined, single, and straight nanorods. Destruction of the mask results in selective area growth failure, while damage of the substrate surface promotes inclined nanorods grown into the openings, owning to random oriented nucleation.
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