Marian Varga

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.

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.

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.

Design and investigation of properties of nanocrystalline diamond optical planar waveguides

Diamond thin films have remarkable properties comparable with natural diamond. Because of these properties it is a very promising material for many various applications (sensors, heat sink, optical mirrors, chemical and radiation wear, cold cathodes, tissue engineering, etc.) In this paper we report about design, deposition and measurement of properties of optical planar waveguides fabricated from nanocrystalline diamond thin films. The nanocrystalline diamond planar waveguide was deposited by microwave plasma enhanced chemical vapor deposition and the structure of the deposited film was studied by scanning electron microscopy and Raman spectroscopy. The design of the presented planar waveguides was realized on the bases of modified dispersion equation and was schemed for 632.8 nm, 964 nm, 1 310 nm and 1 550 nm wavelengths. Waveguiding properties were examined by prism coupling technique and it was found that the diamond based planar optical element guided one fundamental mode for all measured wavelengths. Values of the refractive indices of our NCD thin film measured at various wavelengths were almost the same as those of natural diamond.

Diamond photonic crystal slab: leaky modes and modified photoluminescence emission of surface-deposited quantum dots.

Detailed analysis of a band diagram of a photonic crystal (PhC) slab prepared on a nano-diamond layer is presented. Even though the PhC is structurally imperfect, the existence of leaky modes, determined both theoretically and experimentally in the broad spectral region, implies that an efficient light interaction with a material periodicity occurs in the sample. It is shown that the luminescence emission spectrum of a light source placed directly on the PhC surface can be modified by employing the optical modes of the studied structure. We stress also the impact of intrinsic optical losses of the nano-diamond on this modification.

Influence of non-diamond carbon phase on recombination mechanisms of photoexcited charge carriers in microcrystalline and nanocrystalline diamond studied by time resolved photoluminescence spectroscopy

Recombination processes of photoexcited charge carriers in as-grown micro/nanocrystalline diamond films containing various amounts of non-diamond carbon phase were studied by time resolved photoluminescence spectroscopy. The photoluminescence was found to be strongly sensitive to diamond morphology and concentration of non-diamond carbon phase. We found two photoluminescence components differing in decay rates (nano/microsecond time scales) and in response to ambient air pressure, temperature and excitation light parameters. Experimental data form the basis for interpretation of recombination paths of photoexcited charge carriers in micro/nanocrystalline diamond films in dependence on their morphology and non-diamond carbon phase content.

Coherent phonon dynamics in micro- and nanocrystalline diamond

We report on the time-resolved coherent anti-Stokes Raman spectroscopy of phonon dephasing in micro- and nanocrystalline diamond films. The dephasing times T(2) were found to be dependent on the morphology of diamond films (average size of crystals and content of nondiamond carbon phase) and changed from 0.7 to 1.72 ps. The dephasing times were found to be temperature independent in the range 10-295 K. In addition to diamond Raman active phonon mode at 1332 cm(-1), we investigated also the dynamics of a broad Raman peak at 1530 cm(-1) which is present in samples with higher content of nondiamond sp(2) hybridized carbon phase. This peak was found to be homogenously broadened with very fast dephasing (T(2)~50 fs).

Two-dimensional photonic crystal slab with embedded silicon nanocrystals: Efficient photoluminescence extraction

A two-dimensional photonic crystal (PhC) slab was fabricated from a luminescent planar waveguide, formed by a (800 nm thick) layer of silicon nanocrystals (SiNCs) embedded in a polished silica plate. Dimensions of the PhC were designed so that light emitted by SiNCs under excitation with an external UV source can, during its propagation in the layer, interact with the periodicity and be Bragg-diffracted into air. This approach leads to up to 8-fold vertical extraction enhancement of SiNCs luminescence from the PhC slab compared to the bare planar layer. Results of the experiment are supported by the computer simulation.

Enhanced Extraction of Silicon-Vacancy Centers Light Emission Using Bottom-Up Engineered Polycrystalline Diamond Photonic Crystal Slabs

Silicon vacancy (SiV) centers are optically active defects in diamond. The SiV centers, in contrast to nitrogen vacancy (NV) centers, possess narrow and efficient luminescence spectrum (centered at ≈738 nm) even at room temperature, which can be utilized for quantum photonics and sensing applications. However, most of light generated in diamond is trapped in the material due to the phenomenon of total internal reflection. In order to overcome this issue, we have prepared two-dimensional photonic crystal slabs from polycrystalline diamond thin layers with high density of SiV centers employing bottom-up growth on quartz templates. We have shown that the spectral overlap between the narrow light emission of the SiV centers and the leaky modes extracting the emission into almost vertical direction (where it can be easily detected) can be obtained by controlling the deposition time. More than 14-fold extraction enhancement of the SiV centers photoluminescence was achieved compared to an uncorrugated sample. Computer simulation confirmed that the extraction enhancement originates from the efficient light-matter interaction between light emitted from the SiV centers and the photonic crystal slab.