We report the synthesis of eight new members of the i-MAX family, of the formula (Mo_2/3RE_1/3)₂GaC, where RE = Gd, Tb, Dy, Ho, Er, Tm, Lu, and Yb, the latter not previously incorporated in a MAX phase. The structure and composition of powder samples were investigated by X-ray diffraction, scanning transmission electron microscopy, and energy dispersive X-ray analysis combined with scanning electron microscopy. All phases showed evidence of an orthorhombic (Cmcm) structure, and the phases based on Er and Yb also crystallized in a monoclinic (C2/c) arrangement. The chemical order of the magnetic elements suggests interesting magnetic characteristics, with a high tuning potential through the range of attainable lanthanide elements.

MAX phases are a group of nanolaminated ternary carbides and nitrides, with a composition expressed by the general formula Mn+1AXn (𝑛 = 1 − 3), where M is a transition metal, A is an A-group element, and X is carbon and/or nitrogen. MAX phases have attracted interest due to their unique combination of metallic and ceramic properties, related to their inherently laminated structure of a transition metal carbide (Mn+1Xn) layer interleaved by an A-group metal layer.

This Thesis explores synthesis and characterization of magnetic MAX phases, where the A-group element is gallium (Ga). Due to the low melting point of Ga (T = 30 °C), conventional thin film synthesis methods become challenging, as the material is in liquid form at typical process temperatures. Development of existing methods has therefore been investigated, for reliable/reproducible synthesis routes, including sputtering from a liquid target, and resulting high quality material. Routes for minimizing trial-and-error procedures during optimization of thin film synthesis have also been studied, allowing faster identification of optimal deposition conditions and a simplified transfer of essential deposition parameters between different deposition systems.

A large part of this Thesis is devoted towards synthesis of MAX phase thin films in the Cr-Mn-Ga-C system. First, through process development, thin films of Cr2GaC were deposited by magnetron sputtering. The films were epitaxial, however with small amount of impurity phase Cr3Ga, as confirmed by X-ray diffraction (XRD) measurements. The film structure was confirmed by scanning transmission electron microscopy (STEM) and the composition by energy dispersive X-ray spectroscopy (EDX) inside the TEM.

Inspired by predictive ab initio calculations, the new MAX phase Mn2GaC was successfully synthesized in thin film form by magnetron sputtering. Structural parameters and magnetic properties were analysed. The material was found to have two magnetic transitions in the temperature range 3 K to 750 K, with a first order transition at around 214 K, going from non-collinear antiferromagnetic state at lower temperature to an antiferromagnetic state at higher temperature. The Neél temperature was determined to be 507 K, changing from an antiferromagnetic to a paramagnetic state. Above 800 K, Mn2GaC decomposes. Furthermore, magnetostrictive, magnetoresistive and magnetocaloric properties of the material were iv determined, among which a drastic change in lattice parameters upon the first magnetic transition was observed. This may be of interest for magnetocaloric applications.

Synthesis of both Cr2GaC and Mn2GaC in thin film form opens the possibility to tune the magnetic properties through a solid solution on the transition metal site, by alloying the aforementioned Cr2GaC with Mn, realizing (Cr1-xMnx)2GaC. From a compound target with a Cr:Mn ratio of 1:1, thin films of (Cr0.5Mn0.5)2GaC were synthesized, confirmed by TEM-EDX. Optimized structure was obtained by deposition on MgO substrates at a deposition temperature of 600 ºC. The thin films were phase pure and of high structural quality, allowing magnetic measurements. Using vibrating sample magnetometry (VSM), it was found that (Cr0.5Mn0.5)2GaC has a ferromagnetic component in the temperature range from 30 K to 300 K, with the measured magnetic moment at high field decreasing by increasing temperature. The remanent moment and coercive field is small, 0.036 μB, and 12 mT at 30 K, respectively. Using ferromagnetic resonance spectroscopy, it was also found that the material has pure spin magnetism, as indicated by the determined spectroscopic splitting factor g = 2.00 and a negligible magnetocrystalline anisotropy energy.

Fuelled by the recent discoveries of in-plane chemically ordered quaternary MAX phases, so called i-MAX phases, and guided by ab initio calculations, new members within this family, based on Cr and Mn, were synthesized by pressureless sintering methods, realizing (Cr2/3Sc1/3)2GaC and (Mn2/3Sc1/3)2GaC. Their structural properties were determined. Through these phases, the Mn content is the highest obtained in a bulk MAX phase to date.

This work has further developed synthesis processes for sputtering from liquid material, for an optimized route to achieve thin films of controlled composition and a high structural quality. Furthermore, through this work, Mn has been added as a new element in the family of MAX phase elements. It has also been shown, that alloying with different content of Mn gives rise to varying magnetic properties in MAX phases. As a result of this Thesis, it is expected that the MAX phase family can be further expanded, with more members of new compositions and new properties.

An inherent property of cathodic arc is the generation of macroparticles, of a typical size ranging from submicrometer up to a few tens of mu m. In this work, we have studied macroparticle generation from a Mo0.78Cu0.22 cathode used in a dc vacuum arc discharge, and we present evidence for super-size macroparticles of up to 0.7mm in diameter. All analyzed particles are found to be rich in Mo (>= 98 at. %). The particle generation is studied by visual observation of the cathode surface during arcing, by analysis of composition and geometrical features of the used cathode surface, and by examination of the generated macroparticles with respect to shape and composition. A mechanism for super-size macroparticle generation is suggested based on observed segregated layers of Mo and Cu identified in the topmost part of the cathode surface, likely due to the discrepancy in melting and evaporation temperatures of Mo and Cu. The results are of importance for increasing the fundamental understanding of macroparticle generation, which in turn may lead to increased process control and potentially provide paths for tuning, or even mitigating, macroparticle generation. (C) 2016 AIP Publishing LLC.

Inherently layered magnetic materials, such as magnetic M(n+1)AX(n) (MAX) phases, offer an intriguing perspective for use in spintronics applications and as ideal model systems for fundamental studies of complex magnetic phenomena. The MAX phase composition M(n+1)AX(n) consists of M(n+1)AX(n) blocks separated by atomically thin A-layers where M is a transition metal, A an A-group element, X refers to carbon and/or nitrogen, and n is typically 1, 2, or 3. Here, we show that the recently discovered magnetic Mn2GaC MAX phase displays structural changes linked to the magnetic anisotropy, and a rich magnetic phase diagram which can be manipulated through temperature and magnetic field. Using first-principles calculations and Monte Carlo simulations, an essentially one-dimensional (1D) interlayer plethora of two-dimensioanl (2D) Mn-C-Mn trilayers with robust intralayer ferromagnetic spin coupling was revealed. The complex transitions between them were observed to induce magnetically driven anisotropic structural changes. The magnetic behavior as well as structural changes dependent on the temperature and applied magnetic field are explained by the large number of low energy, i.e., close to degenerate, collinear and noncollinear spin configurations that become accessible to the system with a change in volume. These results indicate that the magnetic state can be directly controlled by an applied pressure or through the introduction of stress and show promise for the use of Mn2GaC MAX phases in future magnetoelectric and magnetocaloric applications.

Thin films deposited with unfiltered DC arc plasma from Ti, Ti0.75Al0.25, Ti0.50Al0.50, Ti0.30Al0.70, and Al cathodes were characterized with a scanning electron microscope for quantification of extent of macroparticle incorporation. Depositions were performed in N-2 atmosphere in the pressure range from 10(-6) Torr up to 3 . 10(-2) Torr, and the formation of cathode surface nitride contamination was identified from X-ray diffraction analysis. Visual observation and photographic fixation of the arc spot behavior was simultaneously performed. A reduction in macroparticle generation with decreasing Al content and increasing N-2 pressure was demonstrated. A correlated transformation of the arc from type 2 to the type 1 was visually detected and found to be a function of N-2 pressure and at of Al in the cathode. For the Ti cathode, no arc transformation was detected. These observations can be explained by a comparatively high electrical resistivity and high melting point of Al rich surface nitrides, promoting an arc transformation and a reduction in macropartide generation. (C) 2015 Elsevier B.V. All rights reserved.

Magnetic MAX phase (Cr0.5Mn0.5)(2)GaC thin films grown epitaxially on MgO(111) substrates were studied by ferromagnetic resonance at temperatures between 110 and 300 K. The spectroscopic splitting factor g = 2.00 +/- 0.01 measured at all temperatures indicates pure spin magnetism in the sample. At all temperatures we find the magnetocrystalline anisotropy energy to be negligible which is in agreement with the identified pure spin magnetism.

Growth of (Cr_0.5Mn_0.5)₂GaC thin films from C, Ga, and compound Cr_0.5Mn_0.5 targets is reported for depositions on MgO (111), 4H-SiC (0001), and Al₂O₃ (0001) with and without a NbN (111) seed layer. Structural quality is found to be highly dependent on the choice of substrate with MgO (111) giving the best results as confirmed by X-ray diffraction and transmission electron microscopy. Phase pure, high crystal quality MAX phase thin films are realized, with a Cr:Mn ratio of 1:1. Vibrating sample magnetometry shows a ferromagnetic component from 30 K up to 300 K, with a measured net magnetic moment of 0.67 μ_B per metal (Cr + Mn) atom at 30 K and 5 T. The temperature dependence of the magnetic response suggests competing magnetic interactions with a resulting non-collinear magnetic ordering.

The phase stability of Mon +1GaCn has been investigated using ab-initio calculations. The results indicate stability for the Mo2GaC phase only, with a formation enthalpy of 0.4 meV per atom. Subsequent thin film synthesis of Mo2GaC was performed through magnetron sputtering from elemental targets onto Al2O3 [0001], 6H-SiC [0001] and MgO [111] substrates within the temperature range of 500 degrees C and 750 degrees C. High structural quality films were obtained for synthesis on MgO [111] substrates at 590 degrees C. Evaluation of transport properties showed a superconducting behavior with a critical temperature of approximately 7 K, reducing upon the application of an external magnetic field. The results point towards the first superconducting MAX phase in thin film form.

We have studied the utilization of TiB2 cathodes for thin film deposition in a DC vacuum arc system. We present a route for attaining a stable, reproducible, and fully ionized plasma flux of Ti and B by removal of the external magnetic field, which leads to dissipation of the vacuum arc discharge and an increased active surface area of the cathode. Applying a magnetic field resulted in instability and cracking, consistent with the previous reports. Plasma analysis shows average energies of 115 and 26 eV, average ion charge states of 2.1 and 1.1 for Ti and B, respectively, and a plasma ion composition of approximately 50% Ti and 50% B. This is consistent with measured resulting film composition from X-ray photoelectron spectroscopy, suggesting a negligible contribution of neutrals and macroparticles to the film growth. Also, despite the observations of macroparticle generation, the film surface is very smooth. These results are of importance for the utilization of cathodic arc as a method for synthesis of metal borides. (C) 2015 AIP Publishing LLC.

We have used first-principles calculations and Heisenberg Monte Carlo simulations to search for the magnetic ground state of Mn₂GaC, a recently synthesized magnetic nanolaminate. We have, independent on method, identified a range of low energy collinear as well as non-collinear magnetic configurations, indicating a highly frustrated magnetic material with several nearly degenerate magnetic states. An experimentally obtained magnetization of only 0.29 per Mn atom in Mn₂GaC may be explained by canted spins in an antiferromagnetic configuration of ferromagnetically ordered sub-layers with alternating spin orientation, denoted AFM[0001]. Furthermore, low temperature X-ray diffraction show a new basal plane peak appearing upon a magnetic transition, which is consistent with the here predicted change in inter-layer spacing for the AFM[0001] configuration.