¨This Thesis treats the growth and characterization of ternary transition metal nitride thin films. The aim is to probe deep into the Ti-Al-N system and to explore novel Sc-Al-N compounds. Thin films were epitaxially grown by reactive dual magnetron sputtering from elemental targets onto single-crystal substrates. Ion beam analyses were used for compositional analysis and depth profiling. Different X-ray diffraction techniques were employed, ex situ using Cu radiation and in situ during deposition using synchrotron radiation, to achieve information about phases, texture, and thickness of films, and to follow roughness evolution of layers during and after growth. Transmission electron microscopy was used for overview and lattice imaging, and to obtain lattice structure information by electron diffraction.

In the Sc-Al-N system, the perovskite Sc3AlN was for the first time synthesized as a thin film and in single phase, with a unit cell of 4.40 Å. The hardness was found to be 14.2 GPa, the elastic modulus 21 GPa, and the room temperature resistivity 41.2 μΩcm. Cubic solid solutions of Sc_1-xAl_xN can be synthesized with AlN molar fraction up to ~60%. Higher AlN contents yield three different epitaxial relations to ScN(111), namely, #1 Sc_1-xA_lxN(0001) || ScN(111) with Sc_1-xAl_xN[11210] || ScN[110], #2 Sc_1-xAl_xN(1011) || ScN(110) with Sc_1-xAl_xN[1210] || ScN[110], and #3 Sc_1-xAl_xN(1011) || ScN(113). An in situ deposition and annealing study of cubic Sc0.57Al0.43N films showed volume induced phase separation into ScN and wurtzite structure AlN, via nucleation and growth at the domain boundaries. The first indications for phase separation are visible at 1000 °C, and the topotaxial relationship between the binaries after phase separation is AlN(0001) || ScN(001) and AlN<01ɸ10> || ScN <1ɸ10>. This is compared with Ti1-xAlxN, for which an electronic structure driving force leads to spinodal decomposition into isostructural TiN and AlN already at 800 °C. First principles calculations explain the results on a fundamental physics level. Up to ~22% ScN can under the employed deposition conditions be dissolved into wurtzite Sc1-xAlxN films, while retaining a single-crystal structure and with lattice parameters matching calculated values.

In the Ti-Al-N system, the Ti₂AlN phase was synthesized epitaxially by solid state reaction during interdiffusion between sequentially deposited layers of AlN(0001) and Ti(0001). When annealing the sample, N and Al diffused into the Ti layer, forming Ti₃AlN(111) at 400 ºC and Ti₂AlN(0001) at 500 ºC. The Ti₂AlN formation temperature is 175 ºC lower than earlier reported results. Another way of forming Ti₂AlN phase is by depositing understoichiometric TiNx at 800 °C onto Al₂O₃(0001). An epitaxial Ti₂Al(O,N) (0001) oxynitride forms close to the interface between film and substrate through a solid state reaction. Ti4AlN3 was, however, not possible to synthesize when depositing films with a Ti:Al:N ratio of 4:1:3 due to competing reactions. A substrate temperature of 600 ºC yielded an irregularly stacked Ti_n+1AlN_n layered structure because of the low mobility of Al ad-atoms. An increased temperature led to Al deficiency due to outdiffusion of Al atoms, and formation of the Ti₂AlN phase and a Ti_1-xAl_xN cubic solid solution.