Refractory transition-metal diborides (TMB₂), classified as ultra-high temperature ceramics, are promising materials for extreme thermal and chemical environments. There is a growing demand for employing TMB₂ in high-temperature electrodes, advanced nuclear fission reactors, molten metal containment, refractory crucibles, thermocouple protection tubes in steel baths and aluminum reduction cells, reinforcement fibers, solar power, aerospace, and armor applications. Magnetron-sputter-deposited TMB₂ have recently received increasing attention as the next class of hard ceramic protective thin films. These layers usually crystallize in a hexagonal AlB₂ crystal structure (P6/mmm, SG-191) in which B atoms form graphite-like honeycomb sheets between hexagonal-close-packed TM layers. The strong covalent bonding between TM and B atoms as well as within the honeycomb B sheets provides high melting temperature, hardness, and stiffness, while metallic bonding within TM layers results in good electrical and thermal conductivities. However, sputter-deposited TMB₂ films suffer from several critical issues such as boron overstoichiometry, high brittleness, and low oxidation resistance. All of these aspects are addressed in the thesis.

In Paper 1, the common issue with sputter-deposited diboride thin films, i.e. the presence of excess B, is resolved by using high power impulse magnetron sputtering (HiPIMS). The B/Ti ratio in TiBx films, used as a model materials system, is controllably varied from 2.08 to 1.83 by adjusting the HiPIMS pulse length ton, while maintaining the average power and pulse frequency constant. As a result, the peak current density increases from 0.27 to 0.88 A/cm², which leads to an increased gas rarefaction and, hence, higher metal-ion densities in the plasma. Film growth becomes then increasingly controlled by ionized target atoms, rather than neutral species. Since sputter-ejected Ti atoms have a higher probability of being ionized than B atoms, due to their lower first-ionization potential and larger ionization cross-section, the B/Ti ratio in the films decreases a function of target peak current.

While TM diborides are inherently hard, that alone is not sufficient to prevent failure in applications involving high stresses, as hardness is typically accompanied by brittleness. In order to avoid brittle cracking, thin films must be both hard and relatively ductile, which is referred to as high toughness. In Paper 2, it is demonstrated that Zr_1-xTa_xB_y thin films grown by hybrid high-power impulse and DC magnetron co-sputtering (Ta-HiPIMS/ZrB₂-DCMS) with x ≥ 0.2 are not only hard, but also tough. The films with x ≥ 0.2 show a self-organized columnar core/shell nanostructure (see Paper 3), in which crystalline hexagonal Zr-rich stoichiometric Zr_1-xTa_xB₂ cores are surrounded by narrow dense, disordered Ta-rich shells that are B-deficient.

The disordered shells have the structural characteristics of metallic-glass thin films, which exhibit both high strength and toughness. Hence, such a nanostructure combines the benefits of crystalline diboride nanocolumns, providing the high hardness, with the dense metallic-glasslike shells, which give rise to enhanced toughness.

The mechanical properties of Zr_1-xTa_xB_y thin films annealed in Ar atmosphere are studied as a function of annealing temperature T_a up to 1200 °C in Paper 4. In-situ and ex-situ nanoindentation analyses reveal that all films undergo age hardening up to T_a = 800 °C, with the highest hardness achieved for Zr_0.8Ta_0.2B_1.8 (45.5±1.0 GPa). The age hardening, which occurs without any phase separation or decomposition, can be explained by point-defect recovery that enhances chemical bond density. Although hardness decreases at T_a > 800 °C due mainly to recrystallization, column coarsening, and planar defect annihilation, all layers show hardness values above 34 GPa over the entire T_a range.

The oxidation resistance of TiB_x thin films is addressed in Paper 5. In general, TMB₂ suffer from rapid high-temperature oxidation, which is a critical issue for many applications. In this study, it is demonstrated that alloying the films with Al significantly increases the oxidation resistance with only a slight decrease in hardness. Contrary to bulk TiB₂ synthesized by powder metallurgy processes, the oxidation products of TiB₂ thin films do not contain the B₂O₃ oxide scale, which is usually observed below 1000 °C in air, and merely consists of a TiO₂ phase. The enhanced oxidation resistance is attributed to the formation of a dense, protective Al-containing oxide scale, which considerably decreases the oxygen diffusion rate by suppressing the oxidecrystallites coarsening.

To realize the goal of fully multifunctional diborides, Zr_1-xCr_xB_y thin films grown by hybrid Cr-HiPIMS/ZrB₂-DCMS co-sputtering are studied in Paper 6. These layers exhibit a unique combination of high hardness, toughness, wear, oxidation, and corrosion resistance.

The last paper (Paper 7) addresses the issue of efficient energy and resource consumption in industrial processes, which United Nations defines as one of the sustainable development goals. The idea here is to replace the conventionally used thermal-energy flux from resistive heaters with the irradiation by high mass metal ions (Hf⁺), which results in more efficient energy transfer to the deposited layer. We deposited Ti_0.67Hf_0.33B1.7 films using hybrid HfB₂-HiPIMS/TiB₂-DCMS co-sputtering at substrate temperature not exceeding 100 °C. Results reveal that dense layers can be achieved with high hardness values (> 40 GPa) even though no external substrate heating was used during the process.