Anisotropic chemical expansion due to oxygen vacancies in perovskite films.

In scientifically intriguing and technologically important multifunctional ABO3 perovskite oxides, oxygen vacancies are most common defects. They cause lattice expansion and can alter the key functional properties. Here, it is demonstrated that contrary to weak isotropic expansion in bulk samples, oxygen vacancies produce strong anisotropic strain in epitaxial thin films. This anisotropic chemical strain is explained by preferential orientation of elastic dipoles of the vacancies. Elastic interaction of the dipoles with substrate-imposed misfit strain is suggested to define the dipolar orientation. Such elastic behavior of oxygen vacancies is anticipated to be general for perovskite films and have critical impacts on the film synthesis and response functions.

Effect of diamond-like carbon doped with chromium on cell differentiation, immune activation and apoptosis.

Diamond-like carbon (DLC) is a biocompatible material that has many potential biomedical applications, including in orthopaedics. DLC layers doped with Cr at atomic percent (at.%) of 0, 0.9, 1.8, 7.3, and 7.7 at.% were evaluated with reference to their osteoinductivity with human bone marrow mesenchymal stromal cells (hMSCs), immune activation potential with RAW 264.7 macrophage-like cells, and their effect on apoptosis in Saos-2 human osteoblast-like cells and neonatal human dermal fibroblasts (NHDFs). At mRNA level, hMSCs on DLC doped with 0.9 and 7.7 at.% of Cr reached higher maximum values of both RUNX2 and alkaline phosphatase. An earlier onset of mRNA production of type I collagen and osteocalcin was also observed on these samples; they also supported the production of both type I collagen and osteocalcin. RAW 264.7 macrophages were screened using a RayBio™ Human Cytokine Array for cytokine production. 10 cytokines were at a concentration more than 2 × as high as the concentration of a positive control, but the values for the DLC samples were only moderately higher than the values on glass. NHDF cells, but not Saos-2 cells, had a higher expression of pro-apoptotic markers Bax and Bim and a lower expression of anti-apoptotic factor BCL-XL in proportion to the Cr content. Increased apoptosis was also proven by annexin V staining. These results show that a Cr-doped DLC layer with a lower Cr content can act as an osteoinductive material with relatively low immunogenicity, but that a higher Cr content can induce cell apoptosis.

In situ anion-doped epitaxial strontium titanate films.

Misfit strains arising from a film-substrate mismatch can induce novel phases and properties in the epitaxial films of perovskite oxides. Here we employ yet another effect, namely, strain-assisted formation of oxygen vacancies. We demonstrate the misfit-promoted presence of oxygen vacancies and related substitutional incorporation of anion dopants in the epitaxial films of archetypal perovskite oxide SrTiO3. Both the oxygen vacancies and hydrogen or nitrogen dopants are introduced in situ during the pulsed-laser deposition of the films using compressive substrates. The films exhibit peculiar chemical expansion and optical properties, which are consistent with substitutional anion doping.

Thermooptical evidence of carrier-stabilized ferroelectricity in ultrathin electrodeless films.

Ferroelectric films may lose polarization as their thicknesses decrease to a few nanometers because of the depolarizing field that opposes the polarization therein. The depolarizing field is minimized when electrons or ions in the electrodes or the surface/interface layers screen the polarization charge or when peculiar domain configuration is formed. Here, we demonstrate ferroelectric phase transitions using thermooptical studies in ∼5-nm-thick epitaxial Pb0.5Sr0.5TiO3 films grown on different insulating substrates. By comparing theoretical modeling and experimental observations, we show that ferroelectricity is stabilized through redistribution of charge carriers (electrons or holes) inside ultrathin films. The related high-density of screening carriers is confined within a few-nanometers-thick layer in the vicinity of the insulator, thus resembling a two-dimensional carrier gas.

Optical Properties of Ferroelectric Epitaxial K0.5Na0.5NbO3 Films in Visible to Ultraviolet Range.

The complex index of refraction in the spectral range of 0.74 to 4.5 eV is studied by variable-angle spectroscopic ellipsometry in ferroelectric K0.5Na0.5NbO3 films. The 20-nm-thick cube-on-cube-type epitaxial films are grown on SrTiO3(001) and DyScO3(011) single-crystal substrates. The films are transparent and exhibit a significant difference between refractive indices Δn = 0.5 at photon energies below 3 eV. The energies of optical transitions are in the range of 3.15-4.30 eV and differ by 0.2-0.3 eV in these films. The observed behavior is discussed in terms of lattice strain and strain-induced ferroelectric polarization in epitaxial perovskite oxide films.

Antibacterial, cytotoxicity and physical properties of laser--silver doped hydroxyapatite layers.

Hydroxyapatite layers with silver doping from 0.06 at.% to 14 at.% were prepared by laser deposition. The films' physical properties such as morphology, composition, crystallinity, Young's modulus and microhardness were measured. Films were amorphous or polycrystalline in dependence on deposition temperature (from RT to 600 °C). Antibacterial properties were tested using Escherichia coli and Bacillus subtilis cells. The antibacterial efficacy changed with silver doping from 4% to 100%. Cytotoxicity was studied by a direct contact test. Depending on doping and crystallinity the films were either non-toxic or mildly toxic.

d0 ferromagnetic interface between nonmagnetic perovskites.

We use computational and experimental methods to study d(0) ferromagnetism at a charge-imbalanced interface between two perovskites. In SrTiO(3)/KTaO(3) superlattice calculations, the charge imbalance introduces holes in the SrTiO(3) layer, inducing a d(0) ferromagnetic half-metallic 2D hole gas at the interface oxygen 2p orbitals. The charge imbalance overrides doping by vacancies at realistic concentrations. Varying the constituent materials shows ferromagnetism to be a general property of hole-type d(0) perovskite interfaces. Atomically sharp epitaxial d(0) SrTiO(3)/KTaO(3), SrTiO(3)/KNbO(3), and SrTiO(3)/NaNbO(3) interfaces are found to exhibit ferromagnetic hysteresis at room temperature. We suggest that the behavior is due to the high density of states and exchange coupling at the oxygen t(1g) band in comparison with the more studied d band t(2g) symmetry electron gas.

Influence of hydroxyapatite crystallinity on the growth of keratinocytes.

Dental implantology is a field, which has made a great progression recently. The main task nowadays is to shorten the healing period and so improve the comfort for the patients. One possibility how to full fil this task is to coat the surface of the implant. Very promising material seems to be hydroxyapatite, which is a natural component of human body and suitable method is the pulsed laser deposition. In our study we tried to evaluate difference between crystalline and amorphous hydroxyapatite coated dental implants from the biological point of view. We found that the cells were able to adhere to all of our studied samples. The worst proliferation of fibroblasts was found on the amorphous coating, whereas the adhesion was fully comparable with other surfaces. The level of keratinocyte differentiation was the same on both of the studied surfaces.

Study of laser created ZRO2 and hydroxyapatite/ZrO2 films for implantology.

Thin films of ZrO2 and hydroxyapatite/ZrO2 were created by excimer laser ablation on Ti6Al4V substrates. ZrO2 layers were fabricated in vacuum by KrF laser at various substrate temperatures and hydroxyapatite (HA) layers were fabricated in water vapor ambient by ArF laser and in water vapor/argon ambient by KrF excimer laser. Film properties were evaluated by XRD, SEM and WDX methods. The test of mechanical adhesion was proceeded on ZrO2 films. XRD analysis proved the presence of amorphous or crystalline HA in the deposited films. SEM method demonstrated smooth surface covered by droplets for both HA and ZrO2 films. Ca/P ratio of the HA films is higher than that of the natural HA and is within the range of 2.8-3.0. The HA/ZrO2 and ZrO2 samples were tested in vitro for cytotoxicity. The best results were received by the HA/ZrO2 samples in the test of cytotoxicity. Fibroblasts cultivating with HA/ZrO2 samples exhibited subconfluent and confluent growth and showed fibronectin homogenously.