Synthesis and thermoelectric properties of Cr1-xMexN (Me = Mo, V)

Abstract: Among emerging materials systems for thermoelectric applications, the early transition-metal nitrides based on ScN and CrN show unexpectedly promising properties. These properties are determined by high Seebeck coefficient, low thermal conductivity, and high electrical conductivity. There is, however, still a need to improve the thermoelectric properties. One idea is to introduce dopants or alloying elements to alter the concentration, mobility, and/or type of charge carriers, such as in (Cr1-xVx)N. Another is to focus on the different scattering mechanisms, such as to reduce the scattering of electrons and increase the scattering of phonons, thus increasing the electrical conductivity while lowering the thermal conductivity. Electrical conductivity can be altered by grain boundary modifications, such as larger grains as well as metallic inclusions, for a smoother interface for the electrons. Such nanoinclusions could potentially also act as phonon scattering centra. Phonon scattering can also occur by site substitution of isoelectronic but heavier atoms, which could reduce the phonon mean free path while retaining the electrical conductivity. For CrN, the obvious substitutions are Mo or W.This thesis investigates these effects for CrN-based materials, and how to control the growth of them in a DC-magnetron sputtering system.First, an optimization study for CrN was made, here the power was fixed while the temperature and nitrogen content were varied. Second, the effect of in-situ annealing at the deposition temperature was investigated. Here, both films with pure CrN and films with a mix of CrN and Cr2N were annealed. It was found that temperature, pressure, and ambient gas have a large effect on the decomposition of CrN to Cr2N. Third, alloying with V and Mo was implemented. It was found that Mo quickly breaks the rock-salt structure, and for further investigation of CrMoN and Cr(Mo,V)N systems, other deposition methods which allows for lower deposition rates need to be investigated.The sample deemed best was the CrVN-sample, showing a Seebeck coefficient of -141 μV/K, resistivity of 1520 μΩ∙cm and a power factor of 1.3 mW/mK2.