Nanodiamonds (NDs) containing optically active centers have gained significant relevance as the material of choice for biological, optoelectronic, and quantum applications. However, current production methods lag behind their real needs. This study introduces two CVD-based approaches for fabricating NDs with optically active silicon-vacancy (SiV) color centers: bottom-up (BU) and top-down (TD) methods. The BU approach generates nanoporous diamond films with a core-shell structure, while the TD method employs molten-salt thermal etching to create uniform porous structures from nanocrystalline diamond films. Comprehensive characterization using advanced techniques revealed distinct morphologies and optical properties for each approach. The BU method yielded higher-quality diamond phases with top-surface incorporation of SiV centers, while the TD method demonstrated efficient nondiamond phase removal. Ultrasonic disintegration of both porous films produced NDs ranging from 40 to 500 nm, with unique morphologies characteristic of each approach. Photoluminescence measurements confirmed SiV centers (738 nm) in all NDs, exhibiting sensitivity to surface terminations, particularly in BU samples. Temperature-resolved spectroscopy shows the potential of the fabricated NDs for nano thermometry over a wide range of temperatures up to 100 °C. The zero-phonon line shows 0.022 ± 0.003 nm/K sensitivity, while the line width exhibits 0.068 ± 0.004 nm/K broadening. The presented BU and TD methods offer significant advantages over existing techniques, including streamlined production processes, high-yield ND synthesis with tailored properties, and the potential for scalable, cost-effective manufacturing.

• Publikační typ
• časopisecké články MeSH

Nanodiamonds (NDs) are versatile, broadly available nanomaterials with a set of features highly attractive for applications from biology over energy harvesting to quantum technologies. Via synthesis and surface chemistry, NDs can be tuned from the sub-micron to the single-digit size, from conductive to insulating, from hydrophobic to hydrophilic, and from positively to negatively charged surface by simple annealing processes. Such ND diversity makes it difficult to understand and take advantage of their electronic properties. Here we present a systematic correlated study of structural and electronic properties of NDs with different origins and surface terminations. The absolute energy level diagrams are obtained by the combination of optical (UV-vis) and photoelectron (UPS) spectroscopies, Kelvin probe measurements, and energy-resolved electrochemical impedance spectroscopy (ER-EIS). The energy levels and density of states in the bandgap of NDs are correlated with the surface chemistry and structure characterized by FTIR and Raman spectroscopy. We show profound differences in energy band shifts (by up to 3 eV), Fermi level position (from p-type to n-type), electron affinity (from +0.5 eV to -2.2 eV), optical band gap (5.2 eV to 5.5 eV), band gap states (tail or mid-gap), and electrical conductivity depending on the high-pressure, high-temperature and detonation origin of NDs as well as on the effects of NDs' oxidation, hydrogenation, sp2/sp3 carbon phases and surface adsorbates. These data are fundamental for understanding and designing NDs' optoelectrochemical functional mechanisms in diverse application areas.

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• časopisecké články MeSH

Diamond properties down to the quantum-size region are still poorly understood. High-pressure high-temperature (HPHT) synthesis from chloroadamantane molecules allows precise control of nanodiamond size. Thermal stability and optical properties of nanodiamonds with sizes spanning range from <1 to 8 nm are investigated. It is shown that the existing hypothesis about enhanced thermal stability of nanodiamonds smaller than 2 nm is incorrect. The most striking feature in IR absorption of these samples is the appearance of an enhanced transmission band near the diamond Raman mode (1332 cm-1). Following the previously proposed explanation, we attribute this phenomenon to the Fano effect caused by resonance of the diamond Raman mode with continuum of conductive surface states. We assume that these surface states may be formed by reconstruction of broken bonds on the nanodiamond surfaces. This effect is also responsible for the observed asymmetry of Raman scattering peak. The mechanism of nanodiamond formation in HPHT synthesis is proposed, explaining peculiarities of their structure and properties.

• Klíčová slova
• Fano effect, Fourier-transformed infrared spectra, Raman scattering, chloroadamantane, high-pressure high-temperature synthesis, nanodiamond,
• Publikační typ
• časopisecké články MeSH

Apart from the frequently used high-temperature annealing of detonation nanodiamonds (DNDs) in an inert environment, laser irradiation of DNDs in a liquid can be effectively used for onion-like carbon (OLC) formation. Here, we used fully de-aggregated hydrogenated DNDs (H-DNDs) dispersed in ethanol, which were irradiated for up to 60 min using a 532 nm NdYAG laser with an energy of 150 mJ in a pulse (5 J/cm2) at a pulse duration of 10 ns and a repetition rate of 10 Hz. We investigated the DND surface chemistry, zeta potential, and structure as a function of laser irradiation time. Infrared spectroscopy revealed a monotonical decrease in the C-Hx band intensities and an increase of the C-O and C=O features. Transmission electron microscopy (TEM) revealed the formation of OLC, as well as a gradual loss of nanoparticle character, with increasing irradiation time. Surprisingly, for samples irradiated up to 40 min, the typical and unchanged DND Raman spectrum was recovered after their annealing in air at 450 °C for 300 min. This finding indicates the inhomogeneous sp3 to sp2 carbon transformation during laser irradiation, as well as the insensitivity of DND Raman spectra to surface chemistry, size, and transient structural changes.

• Klíčová slova
• Raman spectroscopy, carbon nano-onion, laser, nanodiamond, onion-like carbon, structure, surface chemistry, zeta potential,
• Publikační typ
• časopisecké články MeSH

Nanoscale composite of detonation nanodiamond (DND) and polypyrrole (PPy) as a representative of organic light-harvesting polymers is explored for energy generation, using nanodiamond as an inorganic electron acceptor. We present a technology for the composite layer-by-layer synthesis that is suitable for solar cell fabrication. The formation, pronounced material interaction, and photovoltaic properties of DND-PPy composites are characterized down to nanoscale by atomic force microscopy, infrared spectroscopy, Kelvin probe, and electronic transport measurements. The data show that DNDs with different surface terminations (hydrogenated, oxidized, poly-functional) assemble PPy oligomers in different ways. This leads to composites with different optoelectronic properties. Tight material interaction results in significantly enhanced photovoltage and broadband (1-3.5 eV) optical absorption in DND/PPy composites compared to pristine materials. Combination of both oxygen and hydrogen functional groups on the nanodiamond surface appears to be the most favorable for the optoelectronic effects. Theoretical DFT calculations corroborate the experimental data. Test solar cells demonstrate the functionality of the concept.

• Publikační typ
• časopisecké články MeSH

Plasma chemical surface modification of nanoparticles in gas-liquid type reactors enables a controllable, specific, low-cost, and environmentally friendly alternative to wet chemistry methods or thermal and dry plasma treatments. Here the atmospheric pressure radio-frequency microplasma jet (µ-APPJ) operating with 0.6% O2 in He is used to deliver aqueous oxygen radicals (AOR) to the surface of ∼3 nm hydrogenated detonation nanodiamonds (H-DNDs) suspended in water. The AOR-treated H-DND samples are characterized by FTIR and XPS spectroscopies and by AFM and SEM imaging. The main chemical reaction mechanism is identified as the abstraction of surface hydrogen atoms by O or OH radicals and a consequent attachment of the OH group, thereby increasing concentration of alcohols, carboxyls, and aldehydes on the DND's surface. FTIR spectra reveal also a structural re-arrangement of the surface water on the AOR-treated H-DNDs. Yet zeta-potential of AOR-treated H-DNDs still remains positive (decreases from +45 mV to +30 mV). The chemical modification gives rise to formation of nanoscale chain-like aggregates when AOR-treated H-DNDs are deposited on Si substrate.

• Publikační typ
• časopisecké články MeSH

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.

• Klíčová slova
• Kelvin probe force microscopy, color center, diamond, nanocrystalline diamond, silicon-vacancy center, surface photovoltage,
• Publikační typ
• časopisecké články MeSH