The development of the field of biomaterials engineering is rapid. Various bioactive coatings are created to improve the biocompatibility of substrates used for bone regeneration, which includes formulation of thin zirconia coatings with pro-osteogenic properties. The aim of this study was to assess the biological properties of ZrO 2 thin films grown by Atomic Layer Deposition (ALD) technology (ZrO 2 ALD). Methodology: The cytocompatibility of the obtained layers was analysed using the mice preosteoblastic cell line (MC3T3) characterized by decreased expression of microRNA 21-5p (miR-21-5p) in order to evaluate the potential pro-osteogenic properties of the coatings. The in vitro experiments were designed to determine the effect of ZrO 2 ALD coatings on cell morphology (confocal microscope), proliferative activity (cell cycle analysis) and metabolism, reflected by mitochondrial membrane potential (cytometric-based measurement). Additionally, the influence of layers on the expression of genes associated with cell survival and osteogenesis was studied using RT-qPCR. The following genes were investigated: B-cell lymphoma 2 (Bcl-2), Bcl-2-associated X protein (Bax), p53 and p21, as well as osteogenic markers, i.e. collagen type 1 (Coll-1), osteopontin (Opn), osteocalcin (Ocl) and runt-related transcription factor 2 (Runx-2). The levels of microRNA (miRNA/miR) involved in the regulation of osteogenic genes were determined, including miR-7, miR-21, miR-124 and miR-223. Results: The analysis revealed that the obtained coatings are cytocompatible and may increase the metabolism of pre-osteoblast, which was correlated with increased mitochondrial membrane potential and extensive development of the mitochondrial network. The obtained coatings affected the viability and proliferative status of cells, reducing the population of actively dividing cells. However, in cultures propagated on ZrO 2 ALD coatings, the up-regulation of genes essential for bone metabolism was noted. Discussion: The data obtained indicate that ZrO 2 coatings created using the ALD method may have pro-osteogenic properties and may improve the metabolism of bone precursor cells. Given the above, further development of ZrO 2 ALD layers is essential in terms of their potential clinical application in bone regenerative medicine.
Titanium nitride is a well-known conductive ceramic material that has recently experienced resumed attention because of its plasmonic properties comparable to metallic gold and silver. Thus, TiN is an attractive alternative for modern and future photonic applications that require compatibility with the Complementary Metal-Oxide-Semiconductor (CMOS) technology or improved resistance to temperatures or radiation. This work demonstrates that polycrystalline TiNx films sputtered on silicon at room temperature can exhibit plasmonic properties continuously from 400 nm up to 30 μm. The films’ composition, expressed as nitrogen to titanium ratio x and determined in the Secondary Ion Mass Spectroscopy (SIMS) experiment to be in the range of 0.84 to 1.21, is essential for optimizing the plasmonic properties. In the visible range, the dielectric function renders the interband optical transitions. For wavelengths longer than 800 nm, the optical properties of TiNx are well described by the Drude model modified by an additional Lorentz term, which has to be included for part of the samples. The ab initio calculations support the experimental results both in the visible and infra-red ranges; particularly, the existence of a very low energy optical transition is predicted. Some other minor features in the dielectric function observed for the longest wavelengths are suspected to be of phonon origin.
Low temperature (at 100 • C and below) growth of ZnO thin films by atomic layer deposition (ALD) is demonstrated. Properties of the layers grown with two different oxygen reagents: ozone and water are compared. Diethylzinc (DEZ) was used as metal precursor. Electrical and structural properties of films obtained at several different growth temperatures, ranging from 50 • C to 250 • C were analyzed. It turned out that the film grown in the water-based process at 250 • C and all films grown with ozone have more ordered crystallographic structure with the privileged growth direction (001) perpendicular to the substrate than water-based samples grown in temperatures 100-200 • C. Higher free electron concentration at room temperature was observed for ozone-based samples grown at 100 • C and 150 • C in comparison to water-based samples obtained at the same growth temperature. Low value of resistivity in case of ozone-based samples grown at 100 • C is a promising result, however lower electron mobility requires further optimization.
Atomic layer deposition (ALD) technology has started to attract attention as an efficient method for obtaining bioactive, ultrathin oxide coatings. In this study, using ALD, we have created titanium dioxide (TiO2) layers. The coatings were characterised in terms of physicochemical and biological properties. The chemical composition of coatings, as well as thickness, roughness, wettability, was determined using XPS, XRD, XRR. Cytocompatibillity of ALD TiO2 coatings was accessed applying model of mouse pre-osteoblast cell line MC3T3-E1. The accumulation of transcripts essential for bone metabolism (both mRNA and miRNA) was determined using RT-qPCR. Obtained ALD TiO2 coatings were characterised as amorphous and homogeneous. Cytocompatibility of the layers was expressed by proper morphology and growth pattern of the osteoblasts, as well as their increased viability, proliferative and metabolic activity. Simultaneously, we observed decreased activity of osteoclasts. Obtained coatings promoted expression of Opn, Coll-1, miR-17 and miR-21 in MC3T3-E1 cells. The results are promising in terms of the potential application of TiO2 coatings obtained by ALD in the field of orthopaedics, especially in terms of metabolic- and age-related bone diseases, including osteoporosis.
Background Due to increasing aging of population prevalence of age-related disorders including osteoporosis is rapidly growing. Due to health and economic impact of the disease, there is an urgent need to develop techniques supporting bone metabolism and bone regeneration after fracture. Due to imbalance between bone forming and bone resorbing cells, the healing process of osteoporotic bone is problematic and prolonged. Thus searching for agents able to restore the homeostasis between these cells is strongly desirable. Results In the present study, using ALD technology, we obtained homogeneous, amorphous layer of hafnium (IV) oxide (HfO2). Considering the specific growth rate (1.9Å/cycle) for the selected process at the temperature of 90 °C, we performed the 100 nm deposition process, which was confirmed by measuring film thickness using reflectometry. Then biological properties of the layer were investigated with pre-osteoblast (MC3T3), pre-osteoclasts (4B12) and macrophages (RAW 264.7) using immunofluorescence and RT-qPCR. We have shown, that HfO2 (i) enhance osteogenesis, (ii) reduce osteoclastogenesis (iii) do not elicit immune response and (iv) exert anti-inflammatory effects. Conclusion HfO2 layer can be applied to cover the surface of metallic biomaterials in order to enhance the healing process of osteoporotic bone fracture.
Trends in the behavior of band gaps in short-period superlattices (SLs) composed of CdO and MgO layers were analyzed experimentally and theoretically for several thicknesses of CdO sublayers. The optical properties of the SLs were investigated by means of transmittance measurements at room temperature in the wavelength range 200–700 nm. The direct band gap of {CdO/MgO} SLs were tuned from 2.6 to 6 eV by varying the thickness of CdO from 1 to 12 monolayers while maintaining the same MgO layer thickness of 4 monolayers. Obtained values of direct and indirect band gaps are higher than those theoretically calculated by an ab initio method, but follow the same trend. X-ray measurements confirmed the presence of a rock salt structure in the SLs. Two oriented structures (111 and 100) grown on c- and r-oriented sapphire substrates were obtained. The measured lattice parameters increase with CdO layer thickness, and the experimental data are in agreement with the calculated results. This new kind of SL structure may be suitable for use in visible, UV and deep UV optoelectronics, especially because the energy gap can be precisely controlled over a wide range by modulating the sublayer thickness in the superlattices.
The continuous development of ALD thin films demands ongoing improvements and changes toward fabricating materials with tailored properties that are suitable for different practical applications. Ozone has been recently established as a precursor, with distinct advantages over the alternative oxidizing precursors in the ALDs of advanced dielectric films. This study reports alumina (Al2O3) and hafnia (HfO2) formation using an O3 source and compares the obtained structural and electrical properties. The performed structural examinations of ozone-based materials proved homogenous high-k films with less vacancy levels compared to water-based films. The enhanced structural properties also result in the problematic incorporation of different dopants through the bulk layer. Furthermore, analysis of electrical characteristics of the MIS structures with ALD gate dielectrics demonstrated the improved quality and good insulating properties of ozone-based films. However, further optimization of the ALD technique with ozone is needed as a relatively low relative permittivity characterizes the ultra-thin films.
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