Merging of Bi-Modality of Ultrafast Laser Processing: Heating of Si/Au Nanocomposite Solutions with Controlled Chemical Content.

Ultrafast laser processing possesses unique outlooks for the synthesis of novel nanoarchitectures and their further applications in the field of life science. It allows not only the formation of multi-element nanostructures with tuneable performance but also provides various non-invasive laser-stimulated modalities. In this work, we employed ultrafast laser processing for the manufacturing of silicon-gold nanocomposites (Si/Au NCs) with the Au mass fraction variable from 15% (0.5 min ablation time) to 79% (10 min) which increased their plasmonic efficiency by six times and narrowed the bandgap from 1.55 eV to 1.23 eV. These nanostructures demonstrated a considerable fs laser-stimulated hyperthermia with a Au-dependent heating efficiency (~10-20 °C). The prepared surfactant-free colloidal solutions showed good chemical stability with a decrease (i) of zeta (ξ) potential (from -46 mV to -30 mV) and (ii) of the hydrodynamic size of the nanoparticles (from 104 nm to 52 nm) due to the increase in the laser ablation time from 0.5 min to 10 min. The electrical conductivity of NCs revealed a minimum value (~1.53 µS/cm) at 2 min ablation time while their increasing concentration was saturated (~1012 NPs/mL) at 7 min ablation duration. The formed NCs demonstrated a polycrystalline Au nature regardless of the laser ablation time accompanied with the coexistence of oxidized Au and oxidized Si as well as gold silicide phases at a shorter laser ablation time (<1 min) and the formation of a pristine Au at a longer irradiation. Our findings demonstrate the merged employment of ultrafast laser processing for the design of multi-element NCs with tuneable properties reveal efficient composition-sensitive photo-thermal therapy modality.

Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds.

The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0-30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2-3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp3 component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp3 bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG).

What Are the Key Factors for the Detection of Peptides Using Mass Spectrometry on Boron-Doped Diamond Surfaces?

We investigated the use of boron-doped diamond (BDD) with different surface morphologies for the enhanced detection of nine different peptides by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS). For the first time, we compared three different nanostructured BDD film morphologies (Continuous, Nanograss, and Nanotips) with differently terminated surfaces (-H, -O, and -F) to commercially available Ground Steel plates. All these surfaces were evaluated for their effectiveness in detecting the nine different peptides by MALDI-MS. Our results demonstrated that certain nanostructured BDD surfaces exhibited superior performance for the detection of especially hydrophobic peptides (e.g., bradykinin 1-7, substance P, and the renin substrate), with a limit of detection of down to 2.3 pM. Further investigation showed that hydrophobic peptides (e.g., bradykinin 1-7, substance P, and the renin substrate) were effectively detected on hydrogen-terminated BDD surfaces. On the other hand, the highly acidic negatively charged peptide adrenocorticotropic hormone fragment 18-39 was effectively identified on oxygen-/fluorine-terminated BDD surfaces. Furthermore, BDD surfaces reduced sodium adduct contamination significantly.

Laser-Induced Modification of Hydrogenated Detonation Nanodiamonds in Ethanol.

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.

Ni-mediated reactions in nanocrystalline diamond on Si substrates: the role of the oxide barrier.

Nanocrystalline diamond (NCD) films grown on Si substrates by microwave plasma enhanced chemical vapor deposition (MWPECVD) were subjected to Ni-mediated graphitization to cover them with a conductive layer. Results of transmission electron microscopy including electron energy-loss spectroscopy of cross-sectional samples demonstrate that the oxide layer on Si substrates (∼5 nm native SiO2) has been damaged by microwave plasma during the early stage of NCD growth. During the heat treatment for graphitizing the NCD layer, the permeability or absence of the oxide barrier allow Ni nanoparticles to diffuse into the Si substrate and cause additional solid-state reactions producing pyramidal crystals of NiSi2 and SiC nanocrystals. The latter are found impinged into the NiSi2 pyramids but only when the interfacial oxide layer is absent, replaced by amorphous SiC. The complex phase morphology of the samples is also reflected in the temperature dependence of electrical conductivity, where multiple pathways of the electronic transport dominate in different temperature regions. We present models explaining the observed cascade of solid-state reactions and resulting electronic transport properties of such heterostructures.

Modification of the Surface Properties of Al x Ga1-x N Substrates with Gradient Aluminum Composition Using Wet Chemical Treatments.

The surface properties of biomolecular gradients are widely known to be important for controlling cell dynamics, but there is a lack of platforms for studying them in vitro using inorganic materials. The changes in various surface properties of an Al x Ga1-x N film (0.173 ≤ x ≤ 0.220) with gradient aluminum content were quantified to demonstrate the ability to modify interfacial characteristics. Four wet chemical treatments were used to modify the surface of the film: (i) oxide passivation by hydrogen peroxide, (ii) two-step functionalization with a carboxylic acid following hydrogen peroxide pretreatment, (iii) phosphoric acid etch, and (iv) in situ functionalization with a phosphonic acid in phosphoric acid. The characterization confirmed changes in the topography, nanostructures, and hydrophobicity after chemical treatment. Additionally, X-ray photoelectron spectroscopy was used to confirm that the chemical composition of the surfaces, in particular, Ga2O3 and Al2O3 content, was dependent on both the chemical treatment and the Al content of the gradient. Spectroscopic evaluation showed red shifts in strain-sensitive Raman peaks as the Al content gradually increased, but the same peaks blue-shifted after chemical treatment. Kelvin probe force microscopy measurements demonstrated that one can modify the surface charge using the chemical treatments. There were no predictable or controllable surface charge trends because of the spontaneous oxide-based nanostructured formations of the bulk material that varied based on treatment and were defect-dependent. The reported methodology and characterization can be utilized in future interfacial studies that rely on water-based wet chemical functionalization of inorganic materials.

Covalent Diamond-Graphite Bonding: Mechanism of Catalytic Transformation.

Aberration-corrected transmission electron microscopy of the atomic structure of diamond-graphite interface after Ni-induced catalytic transformation reveals graphitic planes bound covalently to the diamond in the upright orientation. The covalent attachment, together with a significant volume expansion of graphite transformed from diamond, gives rise to uniaxial stress that is released through plastic deformation. We propose a comprehensive model explaining the Ni-mediated transformation of diamond to graphite and covalent bonding at the interface as well as the mechanism of relaxation of uniaxial stress. We also explain the mechanism of electrical transport through the graphitized surface of diamond. The result may thus provide a foundation for the catalytically driven formation of graphene-diamond nanodevices.

Time-Resolved In Situ Spectroscopy During Formation of the GaP/Si(100) Heterointerface.

Though III-V/Si(100) heterointerfaces are essential for future epitaxial high-performance devices, their atomic structure is an open historical question. Benchmarking of transient optical in situ spectroscopy during chemical vapor deposition to chemical analysis by X-ray photoelectron spectroscopy enables us to distinguish between formation of surfaces and of the heterointerface. A terrace-related optical anisotropy signal evolves during pulsed GaP nucleation on single-domain Si(100) surfaces. This dielectric anisotropy agrees well with the one calculated for buried GaP/Si(100) interfaces from differently thick GaP epilayers. X-ray photoelectron spectroscopy reveals a chemically shifted contribution of the P and Si emission lines, which quantitatively corresponds to one monolayer and establishes simultaneously with the nucleation-related optical in situ signal. We attribute that contribution to the existence of Si-P bonds at the buried heterointerface. During further pulsing and annealing in phosphorus ambient, dielectric anisotropies known from atomically well-ordered GaP(100) surfaces superimpose the nucleation-related optical in situ spectra.