Halyna Kozak

Size and Purity Control of HPHT Nanodiamonds down to 1 nm

High-pressure high-temperature (HPHT) nanodiamonds originate from grinding of diamond microcrystals obtained by HPHT synthesis. Here we report on a simple two-step approach to obtain as small as 1.1 nm HPHT nanodiamonds of excellent purity and crystallinity, which are among the smallest artificially prepared nanodiamonds ever shown and characterized. Moreover we provide experimental evidence of diamond stability down to 1 nm. Controlled annealing at 450 °C in air leads to efficient purification from the nondiamond carbon (shells and dots), as evidenced by X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and scanning transmission electron microscopy. Annealing at 500 °C promotes, besides of purification, also size reduction of nanodiamonds down to ∼1 nm. Comparably short (1 h) centrifugation of the nanodiamonds aqueous colloidal solution ensures separation of the sub-10 nm fraction. Calculations show that an asymmetry of Raman diamond peak of sub-10 nm HPHT nanodiamonds can be well explained by modified phonon confinement model when the actual particle size distribution is taken into account. In contrast, larger Raman peak asymmetry commonly observed in Raman spectra of detonation nanodiamonds is mainly attributed to defects rather than to the phonon confinement. Thus, the obtained characteristics reflect high material quality including nanoscale effects in sub-10 nm HPHT nanodiamonds prepared by the presented method.

Superhydrophilic Polystyrene Nanofiber Materials Generating O2(1Δg): Postprocessing Surface Modifications toward Efficient Antibacterial Effect

The surfaces of electrospun polystyrene (PS) nanofiber materials with encapsulated 1% w/w 5,10,15,20-tetraphenylporphyrin (TPP) photosensitizer were modified through sulfonation, radio frequency (RF) oxygen plasma treatment, and polydopamine coating. The nanofiber materials exhibited efficient photogeneration of singlet oxygen. The postprocessing modifications strongly increased the wettability of the pristine hydrophobic PS nanofibers without causing damage to the nanofibers, leakage of the photosensitizer, or any substantial change in the oxygen permeability of the inner bulk of the polymer nanofiber. The increase in the surface wettability yielded a significant increase in the photo-oxidation of external polar substrates and in the antibacterial activity of the nanofibers in aqueous surroundings. The results reveal the crucial role played by surface hydrophilicity/wettability in achieving the efficient photo-oxidation of a chemical substrate/biological target at the surface of a material generating O2((1)Δg) with a short diffusion length.

Polylactide nanofibers with hydroxyapatite as growth substrates for osteoblast-like cells

Various types of nanofibers are increasingly used in tissue engineering, mainly for their ability to mimic the architecture of tissue at the nanoscale. We evaluated the adhesion, growth, viability, and differentiation of human osteoblast-like MG 63 cells on polylactide (PLA) nanofibers prepared by needle-less electrospinning and loaded with 5 or 15 wt % of hydroxyapatite (HA) nanoparticles. On day 7 after seeding, the cell number was the highest on samples with 15 wt % of HA. This result was confirmed by the XTT test, especially after dynamic cultivation, when the number of metabolically active cells on these samples was even higher than on control polystyrene. Staining with a live/dead kit showed that the viability of cells on all nanofibrous scaffolds was very high and comparable to that on control polystyrene dishes. An enzyme-linked immunosorbent assay revealed that the concentration of osteocalcin was also higher in cells on samples with 15 wt % of HA. There was no immune activation of cells (measured by production of TNF-alpha), associated with the incorporation of HA. Moreover, the addition of HA suppressed the creep behavior of the scaffolds in their dry state. Thus, nanofibrous PLA scaffolds have potential for bone tissue engineering, particularly those with 15 wt % of HA.

High-yield fabrication and properties of 1.4 nm nanodiamonds with narrow size distribution.

Detonation nanodiamonds (DNDs) with a typical size of 5 nm have attracted broad interest in science and technology. Further size reduction of DNDs would bring these nanoparticles to the molecular-size level and open new prospects for research and applications in various fields, ranging from quantum physics to biomedicine. Here we show a controllable size reduction of the DND mean size down to 1.4 nm without significant particle loss and with additional disintegration of DND core agglutinates by air annealing, leading to a significantly narrowed size distribution (±0.7 nm). This process is scalable to large quantities. Such molecular-sized DNDs keep their diamond structure and characteristic DND features as shown by Raman spectroscopy, infrared spectroscopy, STEM and EELS. The size of 1 nm is identified as a limit, below which the DNDs become amorphous.

Optical characterisation of organosilane-modified nanocrystalline diamond films

We report on an optical characterisation of nanocrystalline diamond films photochemically functionalised with the organosilane-coupling agent, N1-(3-(trimethoxysilyl)propyl)hexane-1,6-diamine (alternative names: N-(6-aminohexyl)aminopropyl-trimethoxysilane, (3-(6-aminohexylamino)propyl) trimetoxysilane, AHAPS). The presence and homogeneity of the organosilane layers were detected by fluorescence microscopy and infrared reflectance-absorbance spectroscopy. The results indicated that a homogeneous surface coverage with organosilane layers was achieved on diamond surfaces which were modified either by hydrogen or by oxygen plasma treatment. The functionalised nanocrystalline diamonds present a promising solution in future biosensor applications.

Filamentation of diamond nanoparticles treated in underwater corona discharge

Diamond nanoparticles (DNPs), also known as nanodiamonds, have attracted significant interest in recent years due to a number of potential applications. Their particular usage requires proper surface engineering. In this work, DNPs with a nominal diameter of 5 nm were treated using underwater pulsed streamer corona discharge. A reactor with a needle-to-plate electrode system was employed. The electrolytic conductivity of aqueous DNPs suspensions (0.37 g l−1) was adjusted by NaCl to 100 and 500 μS cm−1. The discharge-treated particles predominantly formed several mm long filaments consisting of agglomerates with submicron diameter, independent of the solution conductivity and the treatment time. The treatment of DNPs decreased the sp2-bonded carbon atoms, as evaluated by XPS for more conductive solution. For both solutions, oxidation of the DNP surface was observed. FTIR measurements showed evolution of new bands at 800–950 cm−1 and 1261 cm−1, which were attributed to the formation of epoxides via the attack of HO2˙ radicals on surface CC double bonds.

Nanostructured diamond layers enhance the infrared spectroscopy of biomolecules.

We report on the fabrication and practical use of high-quality optical elements based on Au mirrors coated with diamond layers with flat, nanocolumnar, and nanoporous morphologies. Diamond layers (100 nm thickness) are grown at low temperatures (about 300 °C) from a methane, carbon dioxide, and hydrogen gas mixture by a pulsed microwave plasma system with linear antennas. Using grazing angle reflectance (GAR) Fourier transform infrared spectroscopy with p-polarized light, we compare the IR spectra of fetal bovine serum proteins adsorbed on diamond layers with oxidized (hydrophilic) surfaces. We show that the nanoporous diamond layers provide IR spectra with a signal gain of about 600% and a significantly improved sensitivity limit. This is attributed to its enhanced internal surface area. The improved sensitivity enabled us to distinguish weak infrared absorption peaks of <10-nm-thick protein layers and thereby to analyze the intimate diamond-molecule interface.

Evaluation of Semiinsulating Annealed InP:Ta for Radiation Detectors

InP crystals were grown by the Czochralski technique. They were purified by inclusion of Ta into the growth melt and then converted to the semiinsulating state by annealing. Various annealing regimes were examined to find the optimum material for radiation detectors. Temperature dependent Hall measurements were carried over the range from 300 to 430 K and the activation energy of the impurity responsible for the semiinsulating state was determined from the slope of a straight line plot to be 0.75 eV from the conduction band edge. This energy is different from the activation energy, 0.65 eV, of Fe2+ in InP which was observed for annealed InP grown with an admixture of Fe. An InP wafer selected for fabrication of prototype particle detectors was lapped and chemomechanically polished on the both sides to a final thickness of 0.25 mm. The detectors themselves were fabricated by deposition of circular metal electrodes of 1 mm diameter on both sides of the wafer, using vacuum evaporation of Ni/Ge/Au. The performance of these particle detectors was characterised by pulse-height spectra obtained with alpha particles emitted from 241Am. The maximum of the spectral line measured at 300 K corresponded to an 85% charge collection efficiency when 100 V voltage was applied

CHAPTER 13:Low Temperature Diamond Growth

Diamond thin films represent a class of multi-functional materials whose morphological, chemical, optical and electronic properties can be tailored on demand for specific applications. Nevertheless, this materials versatility inherently requires a high degree of control and understanding of the diamond growth technology. Here, especially, processes at low temperatures become important because of physical limitations regarding the intrinsic properties of typical target substrates (i.e., low melting temperature, high expansion coefficient, high thermal diffusion and chemical reactivity) and compatibility with standard semiconductor industrial technologies. However, low temperature diamond growth (LTDG) is still highly challenging, where novel phenomena are encountered that still remain to be understood. The present chapter focuses on low temperature diamond growth from technological and practical points of view. The LTDG process is divided in two strategies, which are based on i) the modification of the deposition systems and ii) the change of gas chemistry. The state of the art of each strategy and the fundamental growth processes that are involved are reviewed. Among the discussed diamond growth processes, microwave surface wave plasma in linear antenna configuration with oxygen-containing gas mixtures is shown as the most promising process for LTDG over large areas with high optical and electronic grade materials. The growth phenomena observed in linear antenna microwave plasma provide a simple way to control nano- and poly-crystalline diamond character. A practical comparison between focused and linear antenna microwave plasma is presented on several key studies, which utilize LTDG on amorphous silicon, glass, germanium and optical elements used for IR spectroscopy.

FABRICATION AND CHARACTERIZATION OF N-TYPE ZINC OXIDE/P-TYPE BORON DOPED DIAMOND HETEROJUNCTION

Abstract Diamond and ZnO are very promising wide-bandgap materials for electronic, photovoltaic and sensor applications because of their excellent electrical, optical, physical and electrochemical properties and biocompatibility. In this contribution we show that the combination of these two materials opens up the potential for fabrication of bipolar heterojunctions. Semiconducting boron doped diamond (BDD) thin films were grown on Si and UV grade silica glass substrates by HFCVD method with various boron concentration in the gas mixture. Doped zinc oxide (ZnO:Al, ZnO:Ge) thin layers were deposited by diode sputtering and pulsed lased deposition as the second semiconducting layer on the diamond films. The amount of dopants within the films was varied to obtain optimal semiconducting properties to form a bipolar p-n junction. Finally, different ZnO/BDD heterostructures were prepared and analyzed. Raman spectroscopy, SEM, Hall constant and I-V measurements were used to investigate the quality, structural and electrical properties of deposited heterostructures, respectively. I-V measurements of ZnO/BDD diodes show a rectifying ratio of 55 at ±4 V. We found that only very low dopant concentrations for both semiconducting materials enabled us to fabricate a functional p-n junction. Obtained results are promising for fabrication of optically transparent ZnO/BDD bipolar heterojunction.