Stepan Stehlik

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.

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.

Ultrathin Nanocrystalline Diamond Films with Silicon Vacancy Color Centers via Seeding by 2 nm Detonation Nanodiamonds

Color centers in diamonds have shown excellent potential for applications in quantum information processing, photonics, and biology. Here we report chemical vapor deposition (CVD) growth of nanocrystalline diamond (NCD) films as thin as 5-6 nm with photoluminescence (PL) from silicon-vacancy (SiV) centers at 739 nm. Instead of conventional 4-6 nm detonation nanodiamonds (DNDs), we prepared and employed hydrogenated 2 nm DNDs (zeta potential = +36 mV) to form extremely dense (∼1.3 × 1013 cm-2), thin (2 ± 1 nm), and smooth (RMS roughness < 0.8 nm) nucleation layers on an Si/SiOx substrate, which enabled the CVD growth of such ultrathin NCD films in two different and complementary microwave (MW) CVD systems: (i) focused MW plasma with an ellipsoidal cavity resonator and (ii) pulsed MW plasma with a linear antenna arrangement. Analytical ultracentrifuge, infrared and Raman spectroscopies, atomic force microscopy, and scanning electron microscopy are used for detailed characterization of the 2 nm H-DNDs and the nucleation layer as well as the ultrathin NCD films. We also demonstrate on/off switching of the SiV center PL in the NCD films thinner than 10 nm, which is achieved by changing their surface chemistry.

Sensitivity of Diamond-Capped Impedance Transducer to Tröger’s Base Derivative

Sensitivity of an intrinsic nanocrystalline diamond (NCD) layer to naphthalene Trögers base derivative decorated with pyrrole groups (TBPyr) was characterized by impedance spectroscopy. The transducer was made of Au interdigitated electrodes (IDE) with 50 μm spacing on alumina substrate which were capped with the NCD layer. The NCD-capped transducer with H-termination was able to electrically distinguish TBPyr molecules (the change of surface resistance within 30-60 kΩ) adsorbed from methanol in concentrations of 0.04 mg/mL to 40 mg/mL. An exponential decay of the surface resistance with time was observed and attributed to the readsorption of air moisture after methanol evaporation. After surface oxidation the NCD cap layer did not show any leakage due to NCD grain boundaries. We analyzed electronic transport in the transducer and propose a model for the sensing mechanism based on surface ion replacement.

Silicon-Vacancy Centers in Ultra-Thin Nanocrystalline Diamond Films

Color centers in diamond have shown excellent potential for applications in quantum information processing, photonics, and biology. Here we report the optoelectronic investigation of shallow silicon vacancy (SiV) color centers in ultra-thin (7–40 nm) nanocrystalline diamond (NCD) films with variable surface chemistry. We show that hydrogenated ultra-thin NCD films exhibit no or lowered SiV photoluminescence (PL) and relatively high negative surface photovoltage (SPV) which is ascribed to non-radiative electron transitions from SiV to surface-related traps. Higher SiV PL and low positive SPV of oxidized ultra-thin NCD films indicate an efficient excitation—emission PL process without significant electron escape, yet with some hole trapping in diamond surface states. Decreasing SPV magnitude and increasing SiV PL intensity with thickness, in both cases, is attributed to resonant energy transfer between shallow and bulk SiV. We also demonstrate that thermal treatments (annealing in air or in hydrogen gas), commonly applied to modify the surface chemistry of nanodiamonds, are also applicable to ultra-thin NCD films in terms of tuning their SiV PL and surface chemistry.

Surface potential of nanodiamonds investigated by KPFM

Abstract This chapter introduces complex opto-electronic behavior of nanodiamonds when they are in contact with surrounding materials. Kelvin probe force microscopy (KPFM) is used to show that surface potential of nanodiamonds is not uniform but depends on many factors such as substrate and probe material, nanodiamond surface termination, charge trapping, illumination, and adsorbed water. Special attention is devoted to practical aspects and methodology of the KPFM measurements of nanodiamonds and other nanoscale objects, in general. KPFM serves here also as a nanoscale tool for investigation of local charge exchange between the nanodiamonds and surroundings, which is shown to influence also their other physical properties such as photoluminescence, secondary electron emission, and photovoltage.