目的 研究不同成分及组织结构Ti-Nb-Zr-Ta中熵合金薄膜的光热性能及抗菌能力。方法 采用磁控溅射技术,以0°、45°、80°等不同入射角度沉积一系列Ti-Nb-Zr-Ta中熵合金薄膜,并对薄膜成分、元素价态、物相组成、形貌进行表征,测试薄膜的光吸收率和光热转化能力,研究薄膜的生物相容性和抗菌性能。结果 Ti-Nb-Zr-Ta中熵合金薄膜晶体结构为体心立方结构。随入射角增大,薄膜Ti、Nb含量增加,Zr、Ta含量减少,薄膜的氧含量增加,柱状晶倾斜角度增大,结构变疏松,表面粗糙度增大。由于疏松的柱状晶增加光线的多次反射吸收,以及疏松结构导致的等离子激元共振增强,薄膜的光吸收率增大,光热温度升高。红外光照射薄膜后,薄膜的温度快速上升,入射角为80°沉积的薄膜,经2 W/cm2的808 nm红外光照射3 min后,温度最高达到110 ℃。薄膜整体表现出抗菌能力,红外光照射入射角为80°沉积的薄膜10 min后,表面附着菌落被完全杀死。薄膜整体表现出优异的生物相容性,成纤维细胞可在其表面自然增殖。结论 斜入射磁控溅射沉积的Ti-Nb-Zr-Ta中熵合金薄膜,因其疏松柱状晶形成的“光陷阱”结构,提升了薄膜的光热性能,使薄膜呈现出光热抗菌能力。
Abstract
Ti-Nb-Zr-Ta medium entropy alloys (MEAs) are promising for implantable devices due to their excellent biocompatibility, corrosion resistance, and low metal-ion release. Yet a persistent limitation of this alloy family is the lack of intrinsic antibacterial activity, which leaves implanted devices vulnerable to biofilm formation and infection. The micro/nanostructured Ti-Nb-Zr-Ta MEA films were developed by oblique-angle (glancing-angle) magnetron sputtering (OAD/GLAD) and the resulting coatings exhibited light-activated photothermal antibacterial activity. The examination was carried out on how deposition geometry controlled composition, crystal structure, and morphology. These features were further linked to optical absorptance, photothermal conversion, and antibacterial efficacy under near-infrared (NIR) irradiation. A series of Ti-Nb-Zr-Ta films were deposited at incident angles of 0°, 45°, and 80° without external substrate heating. Comprehensive characterization was conducted, including chemical composition, elemental oxidation states, phase constitution, and multiscale morphology, together with measurements of optical absorptance, photothermal response, and biological performance (cytocompatibility and antibacterial activity).
Guided by an average valence electron concentration (VEC) of 4.5 and an atomic size mismatch of 9.4%, the alloy system preferentially stabilized a body-centered cubic (BCC) phase. Consistently, all sputtered films crystallized in BCC. The shadowing effect inherent to oblique-angle deposition strongly modulated the diffracting microstructure and the resulting optical-thermal behavior. As the incident angle increased, X-ray diffraction peaks shifted to lower 2θ, broadened in full width at half maximum (FWHM), and diminished in intensity. Concomitantly, compositional analysis revealed a monotonic rise in Ti and Nb contents with a corresponding reduction in Zr and Ta, alongside higher oxygen incorporation. Microstructurally, the columns became increasingly tilted and porous with the increasing incident angle. This trend arose from flux self-shadowing during OAD. Incoming species preferentially deposited on target-facing facets, while opposite facets remained shadowed. Limited adatom diffusion at ambient substrate temperature precluded efficient backfilling of these shadowed regions, thereby promoting inclined columnar growth, a looser film network, and increased surface roughness. At an incident angle of 80°, the mean column-substrate angle decreased to 43°, and the root-mean-square roughness increased to 4.97 nm, confirming the emergence of an open, high-surface-area columnar topology.
These OAD-induced structural features translated into markedly enhanced photothermal behavior through a synergistic set of mechanisms. Firstly, hybridization among Ti, Nb, Zr, and Ta increased the electronic density of states. Secondly, the porous, tilted-column morphology acted as an efficient optical-trap scaffold that drove multiple internal reflections and prolonged optical path lengths. Thirdly, increased oxidation at higher deposition angles suppressed specular reflectance and transmittance, further raising effective absorptance. Fourthly, the loose nanoscale architecture strengthened localized plasmonic resonances and dissipative losses, converting more photon energy into heat. As a result, the films showed fast NIR-I photothermal heating. Under 808 nm irradiation (2 W/cm2), the 80° film reached 110 ℃ within 3 min. Importantly, the intrinsic biological inertness of Ti, Nb, Zr, and Ta underpinned excellent biocompatibility across all samples. Leveraging the light-trapping architecture and higher oxidation degree, the high-angle films displayed potent photothermal antibacterial activity. After 10 min of NIR exposure, surface-adherent bacterial colonies on the 80° film were completely eradicated, demonstrating effective on-demand sterilization while maintaining the benign baseline of a bioinert metallic system.
Collectively, these findings establish oblique-angle magnetron sputtering as a facile and scalable route to architected Ti-Nb-Zr-Ta MEA coatings in which deposition geometry serves as a powerful handle to co-tune composition, BCC microstructure, and porous columnar morphology, thereby optimizing broadband optical absorption and heat generation for light-activated antibacterial action. Beyond clarifying the links between flux shadowing, oxygen uptake, and photothermal conversion, this work positions Ti-Nb-Zr-Ta MEA films as compelling candidates for infection-resistant implants and also suggests a general strategy for leveraging geometry-assisted photothermal effects in other bioinert medium-entropy alloys.
关键词
磁控溅射 /
斜入射 /
Ti-Nb-Zr-Ta /
中熵合金 /
光热性能 /
抗菌性能
Key words
magnetron sputtering /
oblique-angle deposition /
Ti-Nb-Zr-Ta /
medium entropy alloy /
photothermal properties /
antibacterial properties
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基金
国家自然科学基金面上项目（52571273）
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