In this study, the effects of substrate temperature and ablation wavelength/mechanism on the structural, mechanical, and bioactivity properties of hydroxyapatite (HA) coatings were investigated. HA coatings were deposited on both Si(100) and Ti6Al4V surfaces. Substrate temperature varied from room temperature to 800 °C. Depositions were performed in Ar/H2O and vacuum environments. X-ray diffraction, scanning electron microscopy, and atomic force microscopy techniques were used to analyze structural and morphological variations. The adherence of coatings to the substrates was assessed by the pull-out method. The obtained data indicated that with the temperature increase, the coatings steadily crystallized. However, temperatures above 700 °C adversely affected protein adsorption and adhesion properties. Similar trends were confirmed via pull-out testing, protein adsorption, and cell proliferation tests. The ablation mechanism was also proven to play an important role in the deposition process. Overall, this study provides further evidence that crystallinity is a vital factor in the functionality of the coatings and depends on the deposition conditions. However, all measurements directly indicated that beyond 700 °C, the morpho-structural, mechanical, and bioactivity properties degrade.
Zirconium (Zr) thin films were deposited on silicon (Si) substrates via pulsed laser deposition (PLD) using a 248 nm excimer laser. The effects of substrate temperature on film morphology and crystallinity were systematically investigated. X-ray diffraction (XRD) revealed that the Zr(100) plane exhibited the strongest orientation at 400 °C while Zr (002) was maximum at 500 °C. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses demonstrated an increase in surface roughness with temperature, with the smoothest surface observed at lower temperatures and significant island formation at 500 °C due to the transition to 3D growth. At 500 °C, interdiffusion effects led to the formation of zirconium silicide at the Zr/Si interface. To further interpret the experimental findings, computational modeling was employed to analyze the transition from 2D layer-by-layer growth to 3D island formation at elevated temperatures. Using a multi-parameter kinetics-free model based on free energy minimization, the critical film thickness for this transition was determined to be ~1–2 nm, aligning well with experimental observations. A separate kinetic model of island nucleation and growth predicts that this shift is driven by the kinetics of adatom surface diffusion. Additionally, the kinetic simulations revealed that, at 400 °C, adatom diffusivity optimally balances crystallization and surface energy minimization, yielding the highest film quality. At 500 °C, the rapid increase in diffusivity leads to the proliferation of 3D islands, consistent with the roughness trends observed in SEM and AFM data. These findings underscore the critical role of deposition parameters in tailoring Zr thin films for applications in advanced coatings and electronic devices.
Zirconium (Zr) thin films were deposited on silicon using pulsed laser deposition (PLD) with two laser wavelengths (1064 nm and 532 nm) and varying substrate temperatures (25 °C, 300 °C, and 500 °C) and laser fluences (0.25, 0.5, 1.0 J/cm2). Results indicate that smoother films were obtained with 1064 nm and surface roughness increased with higher fluences. Optimal crystalline films were obtained at 300 °C. XRD, SEM, and AFM analysis revealed distinct patterns and peaks related to laser parameters. The growth mechanisms of a Zr film were computed based on a well-known continuum model of thin film growth. Our simulations agree with experimental observations. The study highlights crucial factors affecting Zr thin film deposition and provides insights for optimizing PLD parameters to achieve high-quality films.
Zirconia is increasingly favored for dental implants owing to its corrosion resistance, hypoallergenic properties, and superior esthetics, but its biocompatibility remains a challenge. This study explores laser-assisted surface modification to enhance zirconia bioactivity. Zirconia transitions from the monoclinic to the tetragonal phase during sintering, with mixed phases observed in the pre-sintered stage. These transitions are critical for understanding its structural stability and malleability. Grid patterns were imprinted on the green body implant surface using a 1064 nm Nd-YAG laser (Continuum Surelite II, San Jose, CA, USA), with mesh sizes ranging from 7 to 50 µm and depths up to 2 µm, controlled by varying laser fluence, irradiation time, and templates. SEM, AFM, and XRD analyses were used to characterize the surface morphology and crystallography. Protein adsorption studies compared two patterned samples with different surface coverage—the first sample had a patterned area of 0.212 cm2 (27%), while the second sample had a patterned area of 0.283 cm2 (36%)—to a control sample. Protein adsorption increased by 92% in the first and 169% in the second sample, demonstrating a direct correlation between increased pattern area and bioactivity. Enhanced protein adsorption facilitates cell attachment and growth, which are crucial for improving osseointegration. These results underscore the potential of laser-assisted surface modification to optimize zirconia’s performance as a medical implant material.