DLC/TiNi microcage for biopsy applications

A TiNi/diamond-like-carbon (DLC) microcage for biological application has been designed, fabricated and characterized. A compressively stressed DLC film with TiNi pattern on top lifts the fingers upwards once they are released from the substrate, and the microcage can be closed through shape memory effect of top TiNi film with temperature below 80°C. Further heating above 100°C, the gradual opening of the microcage can be obtained due to thermal bimorph effect. The biocompatibility of both the TiNi and DLC films has been proved using a cell-culture method.

Defect and disorder reduction by annealing in hydrogenated tetrahedral amorphous carbon

Hydrogenated tetrahedral amorphous carbon (ta-C:H) is a form of diamond-like carbon with a high sp3 content (>60%), grown here using a plasma beam source. Information on the behaviour of hydrogen upon annealing is obtained from effusion measurements, which show that hydrogen does not effuse significantly at temperatures less than 500 °C in films grown using methane and 700 °C in films grown using acetylene. Raman measurements show no significant structural changes at temperatures up to 300 °C. At higher temperatures, corresponding to the onset of effusion, the Raman spectra show a clustering of the sp2 phase. The density of states of ta-C:H is directly measured using scanning tunnelling spectroscopy. The measured gradients of the conduction and valence band tails increase up to 300 °C, confirming the occurrence of band tail sharpening. Examination of the photoluminescence background in the Raman spectra shows an increase in photoluminescence intensity with decreasing defect density, providing evidence that paramagnetic defects are the dominant non-radiative recombination centres in ta-C:H.

Bonding regimes of nitrogen in amorphous carbon

Nitrogen can have numerous effects on diamond-like carbon: it can dope, it can form the hypothetical superhard compound C3N4, or it can create fullerene-like bonding structures. We studied amorphous carbon nitrogen films deposited by a filtered cathodic vacuum arc as a function of nitrogen content, ion energy and deposition temperature. The incorporation of nitrogen from 10-2 to 10 at% was measured by secondary ion mass spectrometry and elastic recoil detection analysis and was found to vary slightly sublinearly with N2 partial pressure during deposition. In the doping regime from 0 to about 0.4% N, the conductivity changes while the sp3 content and optical gap remain constant. From 0.4 to approximately 10% N, existing sp2 sites condense into clusters and reduce the band gap. Nitrogen contents over 10% change the bonding from mainly sp3 to mainly sp2. Ion energies between 20 and 250 eV do not greatly modify this behaviour. Deposition at higher temperatures causes a sudden loss of sp3 bonding above about 150 °C. Raman spectroscopy and optical gap data show that existing sp2 sites begin to cluster below this temperature, and the clustering continues above this temperature. This transition is found to vary only weakly with nitrogen addition, for N contents below 10%.

Enhancement of microfluidic efficiency with nanocrystalline diamond interlayer in the ZnO-based surface acoustic wave device

Ultra-smooth nanocrystalline diamond (UNCD) films with high-acoustic wave velocity were introduced into ZnO-based surface acoustic wave (SAW) devices to enhance their microfluidic efficiency by reducing the acoustic energy dissipation into the silicon substrate and improving the acoustic properties of the SAW devices. Microfluidic efficiency of the ZnO-based SAW devices with and without UNCD inter layers was investigated and compared. Results showed that the pumping velocities increase with the input power and those of the ZnO/UNCD/Si devices are much larger than those of the ZnO/Si devices at the same power. The jetting efficiency of the droplet was improved by introducing the UNCD interlayer into the ZnO/Si SAW device. Improvement in the microfluidic efficiency is mainly attributed to the diamond layer, which restrains the acoustic wave to propagate in the top layer rather than dissipating into the substrate. © 2013 Springer-Verlag Berlin Heidelberg.

Porous boron-doped diamond/carbon nanotube electrodes.

Nanostructuring boron-doped diamond (BDD) films increases their sensitivity and performance when used as electrodes in electrochemical environments. We have developed a method to produce such nanostructured, porous electrodes by depositing BDD thin film onto a densely packed "forest" of vertically aligned multiwalled carbon nanotubes (CNTs). The CNTs had previously been exposed to a suspension of nanodiamond in methanol causing them to clump together into "teepee" or "honeycomb" structures. These nanostructured CNT/BDD composite electrodes have been extensively characterized by scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Not only do these electrodes possess the excellent, well-known characteristics associated with BDD (large potential window, chemical inertness, low background levels), but also they have electroactive areas and double-layer capacitance values ∼450 times greater than those for the equivalent flat BDD electrodes.

Diamond growth by carbon ion implantation of diamond

Medium energy (5-25 keV) C-13(+) ion implantation into diamond (100) to a fluence ranging from 10(16) cm(-2) to 10(18) cm(-2) was performed for the study of diamond growth via the approach of ion beam implantation. The samples were characterized with Rutherford backscattering/channelling spectroscopy, Raman spectroscopy, X-ray photoemission spectroscopy and Auger electron spectroscopy. Extended defects are formed in the cascade collision volume during bombardment at high temperatures. Carbon incorporation indeed induces a volume growth but the diamond (100) samples receiving a fluence of 4 x 10(17) to 2 x 10(18) at. cm(-2) (with a dose rate of 5 x 10(15) at. cm(-2) s(-1) at 5 to 25 keV and 800 degrees C) showed no He-ion channelling. Common to these samples is that the top surface layer of a few nanometers has a substantial amount of graphite which can be removed by chemical etching. The rest of the grown layer is polycrystalline diamond with a very high density of extended defects.

Single-crystal-like organic heterojunction with 40 nm thick charge accumulation layers

Single-crystal-like organic heterojunction films of copper phthalocyanine (CuPc) and copper-hexadecafluoro-phthalocyanine (F16CuPc) were fabricated by weak-epitaxy-growth method. The intrinsic properties of organic heterojunction were revealed through threshold voltage shift of field-effect transistors and measurement of single-crystal-like diodes. At both sides of the heterojunction interface 40 nm thick charge accumulation layers formed, which showed that the long carriers' diffusion length is due to the high crystallinity and low density of deep bulk traps of single-crystal-like films.

Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

Direct electrochemistry of hemoglobin in egg-phosphatidylcholine films and its catalysis to H2O2

Direct electrochemistry of hemoglobin was observed in stable thin film composed of a natural lipid (egg-phosphatidylcholine) and hemoglobin on pyrolytic graphite (PG) electrode. Hemoglobin in lipid films shows thin layer electrochemistry behavior. The formal potential Edegrees' of hemoglobin in the lipid film was linearly varied with pH in the range from 3.5 to 7.0 with a slope of -46.4 mV pH(-1) Hemoglobin in the lipid film exhibited elegant catalytic activity for electrochemical reduction of H202, based which a unmediated biosensor for H2O2 was developed.

Oxidation of ascorbic acid by rutin at a glassy carbon electrode modified with lipid films

A stable film was prepared by casting dipalmitoylphosphatidylcholine (DPPC) and rutin onto the surface of a glassy carbon (GC) electrode. The electrochemistry behavior of rutin in the DPPC film was investigated. The modified electrode coated with rutin shows a quasi-reversible reduction-oxidation peak on the cyclic voltammogram in phosphate buffer (pH 7.4). This model of biological membrane was not only used to provide biological environment but also to investigate the oxidation of ascorbic acid by rutin. The DPPC-rutin modified electrode behaves as electrocatalytic oxidation to ascorbic acid. The oxidation peak current of ascorbic acid increases drastically and the peak potential of 4 x 10(-4) mol L-1 ascorbic acid shifts negatively about 100 mV compared with that obtained at a bare glassy carbon electrode. The catalytic current increased linearly with the ascorbic acid concentration in the range of 2 x 10(-4) mol L-1 and 1.4 x 10(-3) mol L-1 at a scan rate of 50 mV s(-1).

Interstitial Nitrogen in Diamond – Optical and EPR Studies

Nitrogen is one of the most common impurities in diamond. On a substitutional site it acts as a deep donor, approximately 1.7 eV below the conduction band. Irradiation of nitrogen containing diamond and subsequent annealing creates the nitrogen vacancy centre, which has recently attracted much attention for quantum information processing application. Another possible product of irradiation and annealing of nitrogen containing diamond is interstitial nitrogen. Presumably, a mobile carbon interstitial migrates to a substitutional nitrogen to produce an interstitial nitrogen complex which may or may not be mobile. The configuration(s) of interstitial nitrogen related defects (e.g. bond centred, [001]-split) are not known. An infra-red (IR) absorption peak at 1450 cm-1 labelled H1a has been associated with an nitrogen interstitial complex. [1] Theoretical modelling suggested that this IR local mode is due to a bond centred nitrogen interstitial [2]. However, more recent modelling [3] suggests that this defect is mobile at temperatures were H1a is stable and instead assign H1a to two nitrogen atoms occupying a single lattice site in a [001]-split configuration. To date no electron paramagnetic resonance (EPR) spectra have been conclusively associated with an interstitial nitrogen defect.

In this study we present data from new EPR and optical absorption studies in combination with uniaxial stress of nitrogen interstitial related defects in electron irradiated and annealed nitrogen doped diamond. These measurements yield symmetry information about the defects allowing us to determine which of the proposed models are possible. EPR spectra of nitrogen interstitial related defects in samples isotopically enriched with 15N are reported and we show that these explain the lack of previous EPR data for these defects. Correlations between the IR absorbance and the integrated intensity of the new EPR defects are studied for varying irradiation doses and annealing temperatures.