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Phase formation, thermal stability and magnetic moment of cobalt nitride thin films

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 Added by Mukul Gupta
 Publication date 2015
  fields Physics
and research's language is English




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Cobalt nitride (Co-N) thin films prepared using a reactive magnetron sputtering process by varying the relative nitrogen gas flow (pn) are studied in this work. As pn~increases, Co(N), tcn, Co$_3$N and CoN phases are formed. An incremental increase in pn, after emergence of tcn~phase at pn=10p, results in a continuous expansion in the lattice constant ($a$) of tcn. For pn=30p, $a$ maximizes and becomes comparable to its theoretical value. An expansion in $a$ of tcn, results in an enhancement of magnetic moment, to the extent that it becomes even larger than pure Co. Though such higher (than pure metal) magnetic moment for Fe$_4$N thin films have been theoretically predicted and evidenced experimentally, higher (than pure Co) magnetic moment are evidenced in this work and explained in terms of large-volume high-moment model for tetra metal nitrides.

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In the present work, we systematically studied the effect of Al doping on the phase formation of iron nitride (Fe-N) thin films. Fe-N thin films with different concentration of Al (Al=0, 2, 3, 6, and 12 at.%) were deposited using dc magnetron sputtering by varying the nitrogen partial pressure between 0 to 100%. The structural and magnetic properties of the films were studied using X-ray diffraction and polarized neutron reflectivity. It was observed that at the lowest doping level (2 at.% of Al), nitrogen rich non-magnetic Fe-N phase gets formed at a lower nitrogen partial pressure as compared to the un-doped sample. Interestingly, we observed that as Al doping is increased beyond 3at.%, nitrogen rich non-magnetic Fe-N phase appears at higher nitrogen partial pressure as compared to un-doped sample. The thermal stability of films were also investigated. Un-doped Fe-N films deposited at 10% nitrogen partial pressure possess poor thermal stability. Doping of Al at 2at.% improves it marginally, whereas, for 3, 6 and 12at.% Al doping, it shows significant improvement. The obtained results have been explained in terms of thermodynamics of Fe-N and Al-N.
Single phase nickel-cobalt-titanate thin films with a formula A1+2xTi1-xO3, where A is Ni2+,Co2+ and -0.25<x<1, were grown by pulsed laser deposition on sapphire substrates. There is a large window in which both Ni/Co ratio and x can be chosen independently. In the prototype ilmenite and corundum structures one third of the octahedra are vacant. The reported structure is obtained by filling vacant (x>0) or emptying filled (x<0) octahedra. When x = 1 all octahedra are filled. Two factors controlling the magnetism and crystal distortion are identified. First is a direct overlap between the adjacent cation d-orbitals resulting in a bond formation and magnetic interactions between the cations. This is most clearly revealed as a crystal distortion in the x approximately 0 compositions with approximately equal amounts of Ni and Co: the distortion of the x approximately 0 compound is a function of Ni/Co ratio. The second factor is x, which controls the cation shift towards a vacant octahedron. The displacement decreases and the symmetry increases with decreasing Ti content as was revealed by x-ray diffraction and Raman spectroscopy. When all octahedra are filled the cations prefer octahedron center positions. Also the number density of cations has increased by a factor of 50 percent when compared to the ilmenite structure. The number density ratios of Ni/Co cations between x=1 and x=0 compounds is 3. The Raman and x-ray diffraction data collected on samples with x = 1 or close to 1 are interpreted in terms of P63/mmc space group.
Transition metal dichalcogenides (TMDs) have been a core constituent of 2D material research throughout the last decade. Over this time, research focus has progressively shifted from synthesis and fundamental investigations, to exploring their properties for applied research such as electrochemical applications and integration in electrical devices. Due to the rapid pace of development, priority is often given to application-oriented aspects while careful characterisation and analysis of the TMD materials themselves is occasionally neglected. This can be particularly evident for characterisations involving X-ray photoelectron spectroscopy (XPS), where measurement, peak-fitting, and analysis can be complex and nuanced endeavours requiring specific expertise. To improve the availability and accessibility of reference information, here we present a detailed peak-fitted XPS analysis of ten transition metal chalcogenides. The materials were synthesised as large-area thin-films on SiO2 using direct chalcogenisation of pre-deposited metal films. Alongside XPS, the Raman spectra with several excitation wavelengths for each material are also provided. These complementary characterisation methods can provide a more complete understanding of the composition and quality of the material. As material stability is a crucial factor when considering applications, the in-air thermal stability of the TMDs was investigated after several annealing points up to 400 {deg}C. This delivers a trend of evolving XPS and Raman spectra for each material which improves interpretation of their spectra while also indicating their ambient thermal limits. This provides an accessible library and set of guidelines to characterise, compare, and discuss TMD XPS and Raman spectra.
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The different magnetic behaviors of LaCoO$_3$ films grown on LaAlO$_3$ and SrTiO$_3$ are related to the Co-O-Co bond angles and the constraints imposed on the Co-O bond lengths by the substrate geometries. Long-range magnetic order occurs below T ~ 90 K when the Co-O-Co bond angle is greater than 163 degrees, consistent with the behavior of bulk and nanoparticles forms of LaCoO$_3$. A LaAlO$_3$ substrate prevents magnetic long-range order at low temperatures near the film-substrate interface and collinear antiferromagnetic sublattices away from the interface. At low temperatures, the antiferromagnetically ordered sublattices are non-collinear in films grown on SrTiO$_3$ substrates, leading to a significant net moment.
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