Coatings Functionalization via Laser versus Other Deposition Techniques for Medical Applications: A Comparative Review

The development of new biological devices in response to market demands requires continuous efforts for the improvement of products’ functionalization based upon expansion of the materials used and their fabrication techniques. One viable solution consists of a functionalization substrate covered by layers via an appropriate deposition technique. Laser techniques ensure an enhanced coating’s adherence to the substrate and improved biological characteristics, not compromising the mechanical properties of the functionalized medical device. This is a review of the main laser techniques involved. We mainly refer to pulse laser deposition, matrix-assisted, and laser simple and double writing versus some other well-known deposition methods as magnetron sputtering, 3D bioprinting, inkjet printing, extrusion, solenoid, fuse-deposition modeling, plasma spray (PS), and dip coating. All these techniques can be extended to functionalize surface fabrication to change local morphology, chemistry, and crystal structure, which affect the biomaterial behavior following the chosen application. Surface functionalization laser techniques are strictly controlled within a confined area to deliver a large amount of energy concisely. The laser deposit performances are presented compared to reported data obtained by other techniques

Laser Additive Manufacturing of Bulk Silicon Nitride Ceramic: Modeling versus Integral Transform Technique with Experimental Correlation

A semi-analytical-numerical solution is theorized to describe the laser additive manufacturing via laser-bulk ceramic interaction modeling. The Fourier heat equation was used to infer the thermal distribution within the ceramic sample. Appropriate boundary conditions, including convection and radiation, were applied to the bulk sample. It was irradiated with a Gaussian spatial continuous mode fiber laser (λ = 1.075 µm) while a Lambert-Beer law was assumed to describe the laser beam absorption. A close correlation between computational predictions versus experimental results was validated in the case of laser additive manufacturing of silicon nitride bulk ceramics. The thermal field value rises but stays confined within the irradiated zone due to heat propagation with an infinite speed, a characteristic of the Fourier heat equation. An inverse correlation was observed between the laser beam scanning speed and thermal distribution intensity. Whenever the laser scanning speed increases, photons interact with and transfer less energy to the sample, resulting in a lower thermal distribution intensity. This model could prove useful for the description and monitoring of low-intensity laser beam-ceramic processing

Microstructural Investigations of VO2 Thermochromic Thin Films Grown by Pulsed Laser Deposition for Smart Windows Applications

The structural properties of VO2 thin films, grown on either LSAT or Si substrates by pulsed laser deposition (PLD), are elucidated by means of transmission electron microscopy (TEM) methods. The TEM observations confirmed the successful growth of VO2 by PLD in variable thicknesses, by optimizing the O2 partial pressure and growth temperature. The films adopt a columnar polycrystalline morphology with narrow columns, up to the film thickness height. Four VO2 polymorphs have been detected by electron diffraction and high-resolution TEM (HRTEM) analysis, with M1 being by far the most abundant phase. Post-experimental strain measurements in HRTEM images have revealed that the actual residual strain is minimized due to the columnar morphology of the VO2 grains, as well as intrinsic oxide layers in the VO2/Si epitaxy. The TEM outcomes confirmed the complementary electrical and magnetic measurements in the films, where a transition from a monoclinic M1 to a rutile VO2 R phase has been identified, influenced by the initial percentage of phases in thick VO2 films

Microstructural Investigations of VO₂ Thermochromic Thin Films Grown by Pulsed Laser Deposition for Smart Windows Applications

The structural properties of VO2 thin films, grown on either LSAT or Si substrates by pulsed laser deposition (PLD), are elucidated by means of transmission electron microscopy (TEM) methods. The TEM observations confirmed the successful growth of VO2 by PLD in variable thicknesses, by optimizing the O2 partial pressure and growth temperature. The films adopt a columnar polycrystalline morphology with narrow columns, up to the film thickness height. Four VO2 polymorphs have been detected by electron diffraction and high-resolution TEM (HRTEM) analysis, with M1 being by far the most abundant phase. Post-experimental strain measurements in HRTEM images have revealed that the actual residual strain is minimized due to the columnar morphology of the VO2 grains, as well as intrinsic oxide layers in the VO2/Si epitaxy. The TEM outcomes confirmed the complementary electrical and magnetic measurements in the films, where a transition from a monoclinic M1 to a rutile VO2 R phase has been identified, influenced by the initial percentage of phases in thick VO2 films

Thin Film Fabrication by Pulsed Laser Deposition from TiO2 Targets in O2, N2, He, or Ar for Dye-Sensitized Solar Cells

Active semiconductor layers of TiO2 were synthesized via pulsed laser deposition in He, N2, O2, or Ar to manufacture DSSC structures. As-prepared nanostructured TiO2 coatings grown on FTO were photosensitized by the natural absorption of the N719 (Ruthenium 535-bis TBA) dye to fabricate photovoltaic structures. TiO2 photoanode nanostructures with increased adsorption areas of the photosensitizer (a combination with voluminous media) were grown under different deposition conditions. Systematic SEM, AFM, and XRD investigations were carried out to study the morphological and structural characteristics of the TiO2 nanostructures. It was shown that the gas nature acts as a key parameter of the architecture and the overall performance of the deposited films. The best electro-optical performance was reached for photovoltaic structures based on TiO2 coatings grown in He, as was demonstrated by the short-circuit current (Isc) of 5.40 mA, which corresponds to the higher recorded roughness (of 44 ± 2.9 nm RMS). The higher roughness is thus reflected in a more efficient and deeper penetration of the dye inside the nanostructured TiO2 coatings. The photovoltaic conversion efficiency (η) was 1.18 and 2.32% for the DSSCs when the TiO2 coatings were deposited in O2 and He, respectively. The results point to a direct correlation between the electro-optical performance of the prepared PV cells, the morphology of the TiO2 deposited layers, and the crystallinity features, respectively

Stoichiometry and volume dependent transport in lithium ion memristive devices

LixCoO2, a thoroughly studied cathode material used extensively in Li-ion rechargeable batteries, has recently been proposed as a potential candidate for resistive random access memory and neuromorphic system applications. Memristive cells based on LixCoO2 thin films have been grown on Si substrates and two-probe current-voltage measurements were employed to investigate the origin and nature of resistive switching behavior exhibited by these cells. The results indicate that a voltage-driven metal-to-insulator transition of the active LixCoO2 layer is responsible for the resistive switching behavior, which has a homogeneous nature

Ambiguous Role of Growth-Induced Defects on the Semiconductor-to-Metal Characteristics in Epitaxial VO₂/TiO₂ Thin Films

Controlling the semiconductor-to-metal transition temperature in epitaxial VO₂ thin films remains an unresolved question both at the fundamental as well as the application level. Within the scope of this work, the effects of growth temperature on the structure, chemical composition, interface coherency and electrical characteristics of rutile VO₂ epitaxial thin films grown on TiO₂ substrates are investigated. It is hereby deduced that the transition temperature is lower than the bulk value of 340 K. However, it is found to approach this value as a function of increased growth temperature even though it is accompanied by a contraction along the V⁴⁺–V⁴⁺ bond direction, the crystallographic <i>c</i>-axis lattice parameter. Additionally, it is demonstrated that films grown at low substrate temperatures exhibit a relaxed state and a strongly reduced transition temperature. It is suggested that, besides thermal and epitaxial strain, growth-induced defects may strongly affect the electronic phase transition. The results of this work reveal the difficulty in extracting the intrinsic material response to strain, when the exact contribution of all strain sources cannot be effectively determined. The findings also bear implications on the limitations in obtaining the recently predicted novel semi-Dirac point phase in VO₂/TiO₂ multilayer structures

Synthesis and Anti-Melanoma Activity of L-Cysteine-Coated Iron Oxide Nanoparticles Loaded with Doxorubicin

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe3O4-L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, Mӧssbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe3O4-L-Cys-Dox nanoparticles. Moreover, by means of a FO-SPR sensor, we evidenced and confirmed the binding of Dox to L-Cys. Biological tests on mouse (B16F10) and human (A375) metastatic melanoma cells evidenced the internalization of magnetic nanoparticles delivering Dox. Half maximum inhibitory concentration IC50 values of Fe3O4-L-Cys-Dox were determined for both cell lines: 4.26 µg/mL for A375 and 2.74 µg/mL for B16F10, as compared to 60.74 and 98.75 µg/mL, respectively, for unloaded controls. Incubation of cells with Fe3O4-L-Cys-Dox modulated MAPK signaling pathway activity 3 h post-treatment and produced cell cycle arrest and increased apoptosis by 48 h. We show that within the first 2 h of incubation in physiological (pH = 7.4) media, ~10–15 µM Dox/h was released from a 200 µg/mL Fe3O4-L-Cys-Dox solution, as compared to double upon incubation in citrate solution (pH = 3), which resembles acidic environment conditions. Our results highlight the potential of Fe3O4-L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy

Synthesis and Anti-Melanoma Activity of L-Cysteine-Coated Iron Oxide Nanoparticles Loaded with Doxorubicin

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe3O4-L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, M&#1255;ssbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe3O4-L-Cys-Dox nanoparticles. Moreover, by means of a FO-SPR sensor, we evidenced and confirmed the binding of Dox to L-Cys. Biological tests on mouse (B16F10) and human (A375) metastatic melanoma cells evidenced the internalization of magnetic nanoparticles delivering Dox. Half maximum inhibitory concentration IC50 values of Fe3O4-L-Cys-Dox were determined for both cell lines: 4.26 &micro;g/mL for A375 and 2.74 &micro;g/mL for B16F10, as compared to 60.74 and 98.75 &micro;g/mL, respectively, for unloaded controls. Incubation of cells with Fe3O4-L-Cys-Dox modulated MAPK signaling pathway activity 3 h post-treatment and produced cell cycle arrest and increased apoptosis by 48 h. We show that within the first 2 h of incubation in physiological (pH = 7.4) media, ~10&ndash;15 &micro;M Dox/h was released from a 200 &micro;g/mL Fe3O4-L-Cys-Dox solution, as compared to double upon incubation in citrate solution (pH = 3), which resembles acidic environment conditions. Our results highlight the potential of Fe3O4-L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy