Impact of Ni Doping on the Microstructure and Mechanical Properties of TiB₂ Films

The TiB₂ film exhibits exceptional hardness and chemical stability due to its unique crystal structure and robust covalent bonds, but it also demonstrates high brittleness and poor toughness, which restricts its practical applications in engineering. By appropriately incorporating metal dopants, the toughness of the ceramic matrix can be enhanced without compromising its inherent hardness. In this study, TiB₂ films with different nickel contents (0-32.22 at.%) were fabricated through radio frequency magnetron sputtering. The microstructure, chemical composition, phase structure, and mechanical properties were analyzed using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and nanoindentation tester. The pure TiB₂ film exhibited (0001) and (0002) peaks; however, the addition of nickel resulted in broadening of the (0001) peak and disappearance of the (0002) peak, and no crystalline nickel or other nickel-containing phases could be identified. It was found that the incorporation of nickel refines the grain structure of titanium diboride, with nickel present in an amorphous form at the boundaries of titanium diboride, thereby forming a wrapped structure. The enrichment of nickel at the grain boundary becomes more pronounced as the nickel content is further increased, which hinders the growth of TiB₂ grains, resulting in the thinning of columnar crystals and formation of nanocrystalline in the film, and the coating hardness remains above 20 GPa, when the nickel content is less than 10.83 at.%. With the increase in nickel content, titanium diboride exhibited a tendency to form an amorphous structure, while nickel became increasingly enriched at the boundaries, and the coating hardness and elastic modulus decreased. The wrapped microstructure could absorb the energy generated by compressive shear stress through plastic deformation, which should be beneficial to improve the toughness of the coatings. The addition of nickel enhanced the adhesion between the film and substrate while reducing the friction coefficient of the film. Specifically, when the nickel content reached 4.26 at.%, a notable enhancement in both nanohardness and toughness was observed for nanocomposite films.