Alexander Kromka

Optical properties of nanocrystalline diamond thin films

The optical properties of nanocrystalline diamond films grown from a hydrogen-rich CH4∕H2 gas phase by hot filament chemical vapor deposition, as well as from an argon-rich Ar∕CH4 gas phase by microwave plasma enhanced chemical vapor deposition, are reported. The influence of nitrogen incorporation on the optical absorption is investigated. The diamond films are characterized by photothermal deflection spectroscopy and temperature dependent spectrally resolved photoconductivity. An onset of absorption at about 0.8eV in undoped films is attributed to transitions from π to π states introduced into the band gap by the high amount of sp2 bonded carbon at the grain boundaries. Incorporation of nitrogen leads to a strong absorption in the whole energy spectrum, as a result of the increasing number of sp2 carbon atoms. The effect of surface states has been observed in the high energy region of the spectrum. Transitions to the conduction band tail and photothermal ionization processes account for the observed ons...

Nanoscale topography of nanocrystalline diamonds promotes differentiation of osteoblasts.

The excellent mechanical, tribological and biochemical properties of diamond coatings are promising for improving orthopedic or stomatology implants. A crucial prerequisite for such applications is an understanding and control of the biological response of the diamond coatings. This study concentrates on the correlation of diamond surface properties with osteoblast behavior. Nanocrystalline diamond (NCD) films (grain size up to 200 nm, surface roughness 20 nm) were deposited on silicon substrates of varying roughnesses (1, 270 and 500 nm) and treated by oxygen plasma to generate a hydrophilic surface. Atomic force microscopy was used for topographical characterization of the films. As a reference surface, tissue culture polystyrene (PS) was used. Scanning electron microscopy and immunofluorescence staining was used to visualize cell morphological features as a function of culture time. Metabolic activity, alkaline phosphatase activity, and calcium and phosphate deposition was also monitored. The results show an enhanced osteoblast adhesion as well as increased differentiation (raised alkaline phosphatase activity and mineral deposition) on NCD surfaces (most significantly on RMS 20 nm) compared to PS. This is attributed mainly to the specific surface topography as well as to the biocompatible properties of diamond. Hence the controlled (topographically structured) diamond coating of various substrates is promising for preparation of better implants, which offer faster colonization by specific cells as well as longer-term stability.

Micro-Pattern Guided Adhesion of Osteoblasts on Diamond Surfaces

Microscopic chemical patterning of diamond surfaces by hydrogen and oxygen surface atoms is used for self-assembly of human osteoblastic cells into micro-arrays. The cell adhesion and assembly is further controlled by concentration of cells (2,500-10,000 cells/cm2) and fetal bovine serum (0-15%). The cells are characterized by fluorescence microscopy of actin fibers and nuclei. The serum protein adsorption is studied by atomic force microscopy (AFM). The cells are arranged selectively on O-terminated patterns into 30-200 μm wide arrays. Higher cell concentrations allow colonization of unfavorable H-terminated regions due to mutual cell communication. There is no cell selectivity without the proteins in the medium. Based on the AFM, the proteins are present on both H- and O-terminated surfaces. Pronounced differences in their thickness, surface roughness, morphology, and phase images indicate different conformation of the proteins and explain the cell selectivity.

Enhanced Growth and Osteogenic Differentiation of Human Osteoblast-Like Cells on Boron-Doped Nanocrystalline Diamond Thin Films

Intrinsic nanocrystalline diamond (NCD) films have been proven to be promising substrates for the adhesion, growth and osteogenic differentiation of bone-derived cells. To understand the role of various degrees of doping (semiconducting to metallic-like), the NCD films were deposited on silicon substrates by a microwave plasma-enhanced CVD process and their boron doping was achieved by adding trimethylboron to the CH4:H2 gas mixture, the B∶C ratio was 133, 1000 and 6700 ppm. The room temperature electrical resistivity of the films decreased from >10 MΩ (undoped films) to 55 kΩ, 0.6 kΩ, and 0.3 kΩ (doped films with 133, 1000 and 6700 ppm of B, respectively). The increase in the number of human osteoblast-like MG 63 cells in 7-day-old cultures on NCD films was most apparent on the NCD films doped with 133 and 1000 ppm of B (153,000±14,000 and 152,000±10,000 cells/cm2, respectively, compared to 113,000±10,000 cells/cm2 on undoped NCD films). As measured by ELISA per mg of total protein, the cells on NCD with 133 and 1000 ppm of B also contained the highest concentrations of collagen I and alkaline phosphatase, respectively. On the NCD films with 6700 ppm of B, the cells contained the highest concentration of focal adhesion protein vinculin, and the highest amount of collagen I was adsorbed. The concentration of osteocalcin also increased with increasing level of B doping. The cell viability on all tested NCD films was almost 100%. Measurements of the concentration of ICAM-1, i.e. an immunoglobuline adhesion molecule binding inflammatory cells, suggested that the cells on the NCD films did not undergo significant immune activation. Thus, the potential of NCD films for bone tissue regeneration can be further enhanced and tailored by B doping and that B doping up to metallic-like levels is not detrimental for cells.

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.

Nanoparticles Assume Electrical Potential According to Substrate, Size, and Surface Termination

Electrical potential of nanoparticles under relevant environment is substantial for their applications in electronics as well as sensors and biology. Here, we use Kelvin force microscopy to characterize electrical properties of semiconducting diamond nanoparticles (DNPs) of 5-10 nm nominal size and metallic gold nanoparticles (20 and 40 nm) on Si and Au substrates under ambient conditions. The DNPs are deposited on Si and Au substrates from dispersions with well-defined zeta-potential. We show that the nanoparticle potential depends on its size and that the only reliable potential characteristic is a linear fit of this dependence within a 5-50 nm range. Systematically different potentials of hydrogenated, oxidized, and graphitized DNPs are resolved using this methodology. The differences are within 50 mV, that is much lower than on monocrystalline diamond. Furthermore, all of the nanoparticles assume their potential within -60 mV according to the Au and Si substrate, thus gaining up to 0.4 V difference. This effect is attributed to DNP charging by charge transfer and/or polarization. This is confirmed by secondary electron emission. Such effects are general with broad implications for nanoparticles applications.

Effects of protein inter-layers on cell–diamond FET characteristics

Diamond is recognized as an attractive material for merging solid-state and biological systems. The advantage of diamond field-effect transistors (FET) is that they are chemically resistant, bio-compatible, and can operate without gate oxides. Solution-gated FETs based on H-terminated nanocrystalline diamond films exhibiting surface conductivity are employed here for studying effects of fetal bovine serum (FBS) proteins and osteoblastic SAOS-2 cells on diamond electronic properties. FBS proteins adsorbed on the diamond FETs permanently decrease diamond conductivity as reflected by the -45 mV shift of the FET transfer characteristics. Cell cultivation for 2 days results in a further shift by another -78 mV. We attribute it to a change of diamond material properties rather than purely to the field-effect. Increase in gate leakage currents (by a factor of 4) indicates that the FBS proteins also decrease the diamond-electrolyte electronic barrier induced by C-H surface dipoles. We propose a model where the proteins replace ions in the very vicinity of the H-terminated diamond surface.

Nanofibrous poly(lactide-co-glycolide) membranes loaded with diamond nanoparticles as promising substrates for bone tissue engineering.

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Osteogenic cell differentiation on H-terminated and O-terminated nanocrystalline diamond films.

Nanocrystalline diamond (NCD) films are promising materials for bone implant coatings because of their biocompatibility, chemical resistance, and mechanical hardness. Moreover, NCD wettability can be tailored by grafting specific atoms. The NCD films used in this study were grown on silicon substrates by microwave plasma-enhanced chemical vapor deposition and grafted by hydrogen atoms (H-termination) or oxygen atoms (O-termination). Human osteoblast-like Saos-2 cells were used for biological studies on H-terminated and O-terminated NCD films. The adhesion, growth, and subsequent differentiation of the osteoblasts on NCD films were examined, and the extracellular matrix production and composition were quantified. The osteoblasts that had been cultivated on the O-terminated NCD films exhibited a higher growth rate than those grown on the H-terminated NCD films. The mature collagen fibers were detected in Saos-2 cells on both the H-terminated and O-terminated NCD films; however, the quantity of total collagen in the extracellular matrix was higher on the O-terminated NCD films, as were the amounts of calcium deposition and alkaline phosphatase activity. Nevertheless, the expression of genes for osteogenic markers – type I collagen, alkaline phosphatase, and osteocalcin – was either comparable on the H-terminated and O-terminated films or even lower on the O-terminated films. In conclusion, the higher wettability of the O-terminated NCD films is promising for adhesion and growth of osteoblasts. In addition, the O-terminated surface also seems to support the deposition of extracellular matrix proteins and extracellular matrix mineralization, and this is promising for better osteoconductivity of potential bone implant coatings.

Study of diamond film nucleation by ultrasonic seeding in different solutions

In this study we have investigated diamond nucleation on Si substrates by ultrasonic seeding with different liquid solutions of Ultradispersed Detonation Diamond (UDD) powder in a mixture of metal nano- or microparticles (Ni, Co, Y). The influence of different solutions on nucleation efficiency was investigated. For highlighting nucleation centers and better evaluation of the nucleation process the nucleated samples were moved into a Microwave Plasma Enhanced Chemical Vapor Deposition (MW CVD) reactor and a ”short-time” (10 min), then followed by a ”long-time” (+1 hour), diamond deposition was performed. The morphology of samples was characterized by Scanning Electron Microscopy (SEM) and the chemical composition of grown diamond layer was investigated by Raman Spectroscopy. From the measurements we found out that microsized metal particles positively influenced nucleation and the uniformity of the deposited diamond thin film. The lowest surface roughness was achieved in the case of nanodiamond powder mixed with Co and Y metal powder. The influence of Ni, Co and Y to the nucleation and early growth stage are discussed.