Advanced surface characterization of silver nanocluster segregation in Ag-TiCN bioactive coatings by RBS, GDOES and ARXPS

Surface modification by means of wear protective and antibacterial coatings represents, nowadays, a crucial challenge in the biomaterials field in order to enhance the lifetime of bio-devices. It is possible to tailor the properties of the material by using an appropriate combination of high wear resistance (e.g., nitride or carbide coatings) and biocide agents (e.g., noble metals as silver) to fulfill its final application. This behavior is controlled at last by the outmost surface of the coating. Therefore, the analytical characterization of these new materials requires high-resolution analytical techniques able to provide information about surface and depth composition down to the nanometric level. Among these techniques are Rutherford backscattering spectrometry (RBS), glow discharge optical emission spectroscopy (GDOES), and angle resolved X-ray photoelectron spectroscopy (ARXPS). In this work, we present a comparative RBS–GDOES–ARXPS study of the surface characterization of Ag–TiCN coatings with Ag/Ti atomic ratios varying from 0 to 1.49, deposited at room temperature and 200 °C. RBS analysis allowed a precise quantification of the silver content along the coating with a non-uniform Ag depth distribution for the samples with higher Ag content. GDOES surface profiling revealed that the samples with higher Ag content as well as the samples deposited at 200 °C showed an ultrathin (1–10 nm) Ag-rich layer on the coating surface followed by a silver depletion zone (20–30 nm), being the thickness of both layers enhanced with Ag content and deposition temperature. ARXPS analysis confirmed these observations after applying general algorithm involving regularization in addition to singular value decomposition techniques to obtain the concentration depth profiles. Finally, ARXPS measurements were used to provide further information on the surface morphology of the samples obtaining an excellent agreement with SEM observations when a growth model of silver islands with a height d = 1.5 nm and coverage θ = 0.20 was applied to the sample with Ag/Ti = 1.49 and deposited at room temperature.This work was financially supported by the Spanish Ministry of Science and Innovation (projects FUNCOAT CSD2008-00023 and RyC2007-0026). This research is sponsored by FEDER funds through the program COMPETE "Programa Operacional Factores de Competitividade" and by national funds through FCT "Fundacao para a Ciencia e a Tecnologia", in the framework of the Strategic Projects PEST-C/FIS/UI607/2011, and PEST-C/EME/UI0285/2011 and under the project PTDC/CTM/102853/2008. The authors would like to acknowledge I. Caretti and R. Velasco for the fruitful discussions and the proofreading of the manuscript

Magnetism in one-dimensional quantum dot arrays

We employ the density functional Kohn-Sham method in the local spin-density approximation to study the electronic structure and magnetism of quasi one-dimensional periodic arrays of few-electron quantum dots. At small values of the lattice constant, the single dots overlap, forming a non-magnetic quantum wire with nearly homogenous density. As the confinement perpendicular to the wire is increased, i.e. as the wire is squeezed to become more one-dimensional, it undergoes a spin-Peierls transition. Magnetism sets in as the quantum dots are placed further apart. It is determined by the electronic shell filling of the individual quantum dots. At larger values of the lattice constant, the band structure for odd numbers of electrons per dot indicates that the array could support spin-polarized transport and therefore act as a spin filter.Comment: 11 pages, 6 figure

Ag-Ti(C,N)-based coatings for biomedical applications : influence of silver content on the structural properties

Ag–TiCN coatings were deposited by dc reactive magnetron sputtering and their structural and morphological properties were evaluated. Compositional analysis showed the existence of Ag–TiCN coatings with different Ag/Ti atomic ratios (ranging from 0 to 1.49). The structural and morphological properties are well correlated with the evolution of Ag/Ti atomic ratio. For the samples with low Ag/Ti atomic ratio (below 0.20) the coatings crystallize in a B1-NaCl crystal structure typical of TiC0.3N0.7. The increase in Ag/Ti atomic ratio promoted the formation of Ag crystalline phases as well as amorphous CNx phases detected in both x-ray photoelectron spectroscopy and Raman spectroscopy analysis. Simultaneously to the formation of Ag crystalline phases and amorphous carbon-based phases, a decrease in TiC0.3N0.7 grain size was observed as well as the densification of coatings.Spanish Ministry of Science and InnovationFundação para a Ciência e Tecnologia (FCT)CRUP InstitutionMCIN

Advanced structural characterization of biocompatible Ag-TiCN coatings

One of the main reasons for biomedical implants failure is the generation of wear debris together with microbial infection. To overcome this problem it has been proposed the use of very low wear coatings as diamond-like carbon (DLC), transitionmetal carbides (MeCx) or nitrides (MeNx) in combination with antibacterial elements such silver, gold or copper. The present work explores the potentialities of silver-containing carbon/nitride (Ag-TiCN) based coatings to be used as protective thin films for biomedical implants. Samples were prepared by DC unbalanced reactive magnetron sputtering with contents of Ag ranging from 0 to 20 at.% and Ti from 35 to 15 at.% while keeping C, N and O content constant. The coatings were fully characterized in terms of structure (XRD, Raman) and depth profiling composition by GDOES and RBS (using the nitrogen resonance at 3.70 MeV He+ ions). In particular, we have selected three samples with different Ag contents (0, 6 and 20%) and carried out and advanced surface characterization using XPS, ARXPS and HR-SEM to study the segregation of silver towards the surface. We have correlated the structure and composition of the films with their biological properties. Microbial adhesion was assessed for both bacteria (Staphylococcus epidermidis) and yeast (Candida albicans)

Resonant tunneling through a macroscopic charge state in a superconducting SET transistor

We predict theoretically and observe in experiment that the differential conductance of a superconducting SET transistor exhibits a peak which is a complete analogue in a macroscopic system of a standard resonant tunneling peak associated with tunneling through a single quantum state. In particular, in a symmetric transistor, the peak height is universal and equal to $e^2/2\pi \hbar$. Away from the resonance we clearly observe the co-tunneling current which in contrast to the normal-metal transistor varies linearly with the bias voltage.Comment: 11 pages, 3 figures, Fig. 1 available upon request from the first autho

Magnetic phases of one-dimensional lattices with 2 to 4 fermions per site

We study the spectral and magnetic properties of one-dimensional lattices filled with 2 to 4 fermions (with spin 1/2) per lattice site. We use a generalized Hubbard model that takes account all interactions on a lattice site, and solve the many-particle problem by exact diagonalization. We find an intriguing magnetic phase diagram which includes ferromagnetism, spin-one Heisenberg antiferromagnetism, and orbital antiferromagnetism.Comment: 8 pages, 6 figure

Close-Packing of Clusters: Application to Al_100

The lowest energy configurations of close-packed clusters up to N=110 atoms with stacking faults are studied using the Monte Carlo method with Metropolis algorithm. Two types of contact interactions, a pair-potential and a many-atom interaction, are used. Enhanced stability is shown for N=12, 26, 38, 50, 59, 61, 68, 75, 79, 86, 100 and 102, of which only the sizes 38, 75, 79, 86, and 102 are pure FCC clusters, the others having stacking faults. A connection between the model potential and density functional calculations is studied in the case of Al_100. The density functional calculations are consistent with the experimental fact that there exist epitaxially grown FCC clusters starting from relatively small cluster sizes. Calculations also show that several other close-packed motifs existwith comparable total energies.Comment: 9 pages, 7 figure

Spectral properties of rotating electrons in quantum dots and their relation to quantum Hall liquids

The exact diagonalization technique is used to study many-particle properties of interacting electrons with spin, confined in a two-dimensional harmonic potential. The single-particle basis is limited to the lowest Landau level. The results are analyzed as a function of the total angular momentum of the system. Only at angular momenta corresponding to the filling factors 1, 1/3, 1/5 etc. the system is fully polarized. The lowest energy states exhibit spin-waves, domains, and localization, depending on the angular momentum. Vortices exist only at excited polarized states. The high angular momentum limit shows localization of electrons and separation of the charge and spin excitations.Comment: 14 pages 18 figure

Influence of culture media on the physical and chemical properties of Ag–TiCN coatings

The aim of this study was to verify the possible physical and chemical changes that may occur on the surface of Ag–TiCN coatings after exposure to the culture media used in microbiological and cytotoxic assays, respectively tryptic soy broth (TSB) and Dulbecco's modified eagle's medium (DMEM). After sample immersion for 24 h in the media, analyses were performed by glow discharge optical emission spectroscopy discharge radiation (GDOES), Rutherford backscattering spectroscopy (RBS) and x-ray photoelectron spectroscopy (XPS). The results of GDOES profile, RBS and XPS spectra, of samples immersed in TSB, demonstrated the formation of a thin layer of carbon, oxygen and nitrogen that could be due to the presence of proteins in TSB. After 24 h of immersion in DMEM, the results showed the formation of a thin layer of calcium phosphates on the surface, since the coatings displayed a highly oxidized surface in which calcium and phosphorus were detected. All these results suggested that the formation of a layer on the coating surface prevented the release of silver ions in concentrations that allow antibacterial activity.IC acknowledges the financial support of FCT-Fundacao para a Ciencia e a Tecnologia through the grant SFRH/BD/67022/2009. REG acknowledges support from Ramon y Cajal programme (RyC2007-0026). This research is sponsored by FEDER funds through the program COMPETE-Programa Operacional Factores de Competitividade and by national funds through FCT-Fundacao para a Ciencia e a Tecnologia in the framework of the Strategic Projects PESTC/FIS/UI607/2011, PEST-C/EME/UI0285/2011, PTDC/CTM/102853/2008.The authors thank the FCT Strategic Project PEst-OE/EQB/LA0023/2013 and the Project 'BioHealth-Biotechnology and Bioengineering approaches to improve health quality', Ref. NORTE-07-0124-FEDER-000027, co-funded by the Programa Operacional Regional do Norte (ON.2-O Novo Norte), QREN, FEDER. The authors also thank the project 'Consolidating Research Expertise and Resources on Cellular and Molecular Biotechnology at CEB/IBB', Ref. FCOMP-01-0124-FEDER-027462