Surface characterization of Zr/Ti/Nb tri-layered films deposited by magnetron sputtering on Si(111) and stainless steel substrates

Abstract

Among metallic materials, commercially pure titanium and titanium alloys are very often used as biomaterials for implants. Among these alloys, titanium-aluminum-vanadium alloy Ti-6 A-4 V is one of the most commonly used due to its excellent biocompatibility and ability to allow bone-implant integration. A new class of Ti alloys employs Zr for solid-solution hardening and Nb as β-phase stabilizer. Metals such as Ti, Nb, and Zr—known as valve metals—usually have their surfaces covered by a thin oxide film that forms spontaneously in air. This oxide film constitutes a barrier between the metal and the medium. The Ti-Nb-Zr alloys have mechanical and corrosion resistance characteristics which make them suitable for use as implants. Tri-layered films of Ti-Nb-Zr were deposited on both Si(111) and stainless steel (SS) substrates using dc magnetron sputtering equipment, under an argon atmosphere according to the following methodology: a 100 nm thick layer of Nb was deposited on the substrate, followed by a 200 nm thick layer of Ti, and finally a 50 nm thick layer of Zr, on top of the multilayer stack. The morphology and chemical composition of the films were analyzed by atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). AFM images showed that the Zr/Ti/Nb tri-layer films presented nanostructured grains and low roughness. The ToF-SIMS depth profiles confirmed the formation of a three-layered film on Si(111) with well-defined and sharp interfaces between the layers, while the deposition on the stainless steel substrate caused slight intermixing at the different alloy/Nb, Nb/Ti and Ti/Zr interfaces, reflecting the greater roughness of the raw substrate. The XPS results for the Zr/Ti/Nb layers deposited on Si(111) and SS confirmed that the outermost layer consisted of Zr only, with a predominance of ZrO2, as the metal layer is passivated in air. An oxidation treatment of 1000 °C in air for 1 h for the multilayer stacks caused some dewetting with Si(111) films, and alloying in the layers. The latter effect was more pronounced for the stainless steel substrate.