Permanent reduction of dissipation in nanomechanical Si resonators by chemical surface protection.

We report on mechanical dissipation measurements carried out on thin (∼100 nm), single-crystal silicon cantilevers with varying chemical surface termination. We find that the 1-2 nm-thick native oxide layer of silicon contributes about 85% to the friction of the mechanical resonance. We show that the mechanical friction is proportional to the thickness of the oxide layer and that it crucially depends on oxide formation conditions. We further demonstrate that chemical surface protection by nitridation, liquid-phase hydrosilylation, or gas-phase hydrosilylation can inhibit rapid oxide formation in air and results in a permanent improvement of the mechanical quality factor between three- and five-fold. This improvement extends to cryogenic temperatures. Presented recipes can be directly integrated with standard cleanroom processes and may be especially beneficial for ultrasensitive nanomechanical force- and mass sensors, including silicon cantilevers, membranes, or nanowires.

Structural evolution of Ag-Cu nano-alloys confined between AlN nano-layers upon fast heating.

The structural evolution of a Ag-Cu/AlN nano-multilayer (NML), as prepared by magnetron-sputtering on a α-Al2O3 substrate, was monitored during fast heating by real-time in situ XRD analysis (at the synchrotron), as well as by ex situ microstructural analysis using SEM, XPS and in-house XRD. The as-deposited NML is constituted of alternating nano-layers (thickness ≈ 10 nm) of a chemically inert AlN barrier and a eutectic Ag-Cu(40at%) nano-alloy. The nano-alloy in the as-deposited state is composed of a fcc matrix of Ag nano-grains (≈6 nm), which are supersaturated by Cu, and some smaller embedded Cu rich nano-grains (≈4 nm). Heating up to 265 °C activates segregation of Cu out of the supersaturated Ag nano-grains phase, thus initiating phase separation. At T > 265 °C, the phase-separated Cu metal partially migrates to the top NML surface, thereby relaxing thermally-accumulated compressive stresses in the confined alloy nano-layers and facilitating grain coarsening of (still confined) phase-separated nano-crystallites. Further heating and annealing up to 420 °C results in complete phase separation, forming extended Ag and Cu domains with well-defined coherent Ag/AlN interfaces. The observed outflow of Cu well below the eutectic melting point of the bulk Ag-Cu alloy might provide new pathways for designing low-temperature nano-structured brazing materials.

Negatively charged nitrogen-vacancy centers in a 5 nm thin 12C diamond film.

We report successful introduction of negatively charged nitrogen-vacancy (NV(-)) centers in a 5 nm thin, isotopically enriched ([(12)C] = 99.99%) diamond layer by CVD. The present method allows for the formation of NV(-) in such a thin layer even when the surface is terminated by hydrogen atoms. NV(-) centers are found to have spin coherence times of between T2 ~ 10-100 µs at room temperature. Changing the surface termination to oxygen or fluorine leads to a slight increase in the NV(-) density, but not to any significant change in T2. The minimum detectable magnetic field estimated by this T2 is 3 nT after 100 s of averaging, which would be sufficient for the detection of nuclear magnetic fields exerted by a single proton. We demonstrate the suitability for nanoscale NMR by measuring the fluctuating field from ~10(4) proton nuclei placed on top of the 5 nm diamond film.

Retrospective lifetime estimation of failed and explanted diamond-like carbon coated hip joint balls.

Diamond-like carbon (DLC) coatings are known to have extremely low wear in many technical applications. The application of DLC as a coating has aimed at lowering wear and to preventing wear particle-induced osteolysis in artificial hip joints. In a medical study femoral heads coated with diamond-like amorphous carbon, a subgroup of DLC, articulating against polyethylene cups were implanted between 1993 and 1995. Within 8.5 years about half of the hip joints had to be revised due to aseptic loosening. The explanted femoral heads showed many spots of local coating delamination. Several of these explanted coated TiAlV femoral heads have been analyzed to investigate the reason for this failure. Raman analysis and X-ray photoelectron spectroscopy (XPS) depth profiling showed that the coating consists of diamond-like amorphous carbon, several Si-doped layers and an adhesion-promoting Si interlayer. Focused ion beam (FIB) transverse cuts revealed that the delamination of the coatings is caused by in vivo corrosion of the Si interlayer. Using a delamination test set-up dissolution of the silicon adhesion-promoting interlayer at a speed of more than 100 µm year(-1) was measured in vitro in solutions containing proteins. Although proteins are not directly involved in the corrosion reactions, they can block existing small cracks and crevices under the coating, hindering the exchange of liquid. This results in a build-up of crevice corrosion conditions in the crack, causing a slow dissolution of the Si interlayer.

Tribological behavior of DLC-coated articulating joint implants.

Coatings from diamond-like carbon (DLC) have been proven to be an excellent choice for wear reduction in many technical applications. However, for successful adaption to the total joint replacement field, layer performance, stability and adhesion in realistic physiological setups are quintessential and these aspects have not been consistently researched. In our team's efforts to develop long-term stable DLC implant coatings, test results gained from a simplified linear spinal simulator setup are presented. It is shown that metal-on-metal (MoM) pairs perform well up to 7 million loading cycles, after which they start to generate wear volumes in excess of 20 times those of DLC-coated implants. This is attributed to the roughening observed on unprotected metal surfaces. Furthermore, we illustrate that in contrast to DLC-on-DLC, MoM tribopairs require protein-containing media to establish low-friction conditions. Finally, results of defect monitoring during testing are presented, showing catastrophic failure of layers whose interfaces are too weak with respect to the stress-corrosion-cracking mechanism encountered in vivo.

Chemically patterned, metal oxide based surfaces produced by photolithographic techniques for studying protein- and cell-surface interactions I: Microfabrication and surface characterization.

Chemical patterns on smooth wafer substrates comprising areas with two different metals have been produced by vacuum metal deposition and photolithographic techniques. The combination of metals has been chosen from the series titanium (Ti), aluminium (Al), vanadium (V) and niobium (Nb), producing patterns (dots and stripes with dimensions of 50, 100 and 150 micrometer) with one of the metals as the background and with the second metal (foreground pattern) deposited on the background metal. The structure and chemical composition of the patterned surfaces were evaluated by scanning electron microscopy, X-ray photoelectron spectroscopy and imaging time-of-flight secondary-ion mass spectrometry. The surfaces proved to be geometrically well defined with the expected surface-chemical composition, i.e. a surface oxide (passive) film essentially composed of TiO(2),Al(2)O(3),V(2)O(5), or Nb(2)O(5). Ti/Ti patterned surfaces were produced as controls and found to show no chemical composition contrast. The surface roughness of the pattern was greater than that of the background by a factor of 2-3, but was still extremely smooth with Ra<2nm. The patterns serve as model surfaces for studying in vitro the behaviour of cells as well as the adsorption of serum proteins on different metal oxides, which will be reported in a companion paper. These surfaces can be used to compare and contrast the response of osteoblasts to Ti and other alloy components, such as Al, V, or Nb, which are used in load-bearing medical implants.

Titanium containing amorphous hydrogenated carbon films (a-C: H/Ti): surface analysis and evaluation of cellular reactions using bone marrow cell cultures in vitro.

Amorphous hydrogenated carbon (a-C : H) coatings, also called diamond-like carbon (DLC), have many properties required for a protective coating material in biomedical applications. The purpose of this study is to evaluate a new surface coating for bone-related implants by combining the hardness and inertness of a-C : H films with the biological acceptance of titanium. For this purpose, different amounts of titanium were incorporated into a-C : H films by a combined radio frequency (rf) and magnetron sputtering set-up. The X-ray photoelectron spectroscopy (XPS) of air-exposed a-C : H/titanium (a-C : H/Ti) films revealed that the films were composed of TiO2 and TiC embedded in and connected to an a-C : H matrix. Cell culture tests using primary adult rat bone marrow cell cultures (BMC) were performed to determine effects on cell number and on osteoblast and osteoclast differentiation. By adding titanium to the carbon matrix, cellular reactions such as increased proliferation and reduced osteoclast-like cell activity could be obtained, while these reactions were not seen on pure a-C : H films and on glass control samples. In summary, a-C : H/Ti could be a valuable coating for bone implants, by supporting bone cell proliferation while reducing osteoclast-like cell activation.

The implant material, Ti6Al7Nb: surface microstructure, composition and properties.

The excellent biocompatibility of titanium and its alloys is intimately related with the properties of the surface in contact with the biological environment, and therefore it is closely connected with the stable, passivating oxide layer that forms on its surface. In the present paper, the oxide layer on the alloy Ti6Al7Nb has been characterized using X-ray photoelectron spectroscopy, scanning Auger microscopy and pH-dependent lateral force microscopy. The alloying elements Al and Nb are incorporated in the oxide layer and detected in their most stable oxidized form, as Al2O3 and Nb2O5. Their distribution in the oxide reflects the underlying alpha-beta microstructure, with enrichment of Al in the alpha- and of Nb in the beta-phase (determined by electron microprobe). Friction measurements (lateral force microscopy) indicate slightly different, pH-dependent, lateral forces above the alpha- and beta-phase structures that point to small local variations in surface charges.