One-step synthesis of photoluminescent nanofluids by direct loading of reactively sputtered cubic ZrN nanoparticles into organic liquids.

ZrN nanofluids may exhibit unique optoelectronic properties because of the matching of the solar spectrum with interband transitions and localized surface plasmon resonance (LSPR). Nevertheless, these nanofluids have scarcely been investigated, mainly because of the complexity of the current synthetic routes that involve aggressive chemicals and high temperatures. This work aims to validate reactive dc magnetron sputtering of zirconium in Ar/N2 as an environmentally benign, annealing-free method to produce 22 nm-sized, highly crystalline, stoichiometric, electrically conductive, and plasmonic ZrN nanoparticles (NPs) of cubic shape and to load them into vacuum-compatible liquids of different chemical compositions (polyethylene glycol (PEG), paraffin, and pentaphenyl trimethyl trisiloxane (PTT)) in one step. The nanofluids demonstrate LSPR in the red/near-IR range that gives them a bluish color in transmittance. The nanofluids also demonstrate complex photoluminescence behavior such that ZrN NPs enhance the photoluminescence (PL) intensity of paraffin and PEG, whereas the PL of PTT remains almost invariable. Based on DFT calculations, different energetic barriers to charge transfer between ZrN and the organic molecules are suggested as the main factors that influence the observed optoelectronic response. Overall, our study provides a novel approach to the synthesis of transition metal nitride nanofluids in an environmentally friendly manner, deepens the understanding of the interactions between ZrN and organic molecules, and unveils new optoelectronic phenomena in such systems.

Light emission dynamics of silicon vacancy centers in a polycrystalline diamond thin film.

Diamond thin films can be, at a relatively low-cost, prepared with a high-density of light-emitting negatively charged silicon vacancy (SiV) centers, which opens up the possibility of their application in photonics or sensing. The films are composed of diamond grains with both the SiV centers and sp2-carbon phase, the ratio of these two components being dependent on the preparation conditions. The grain surface and the sp2-related defects might act as traps for the carriers excited within the SiV centers, consequently decreasing their internal photoluminescence (PL) quantum efficiency. Here, we show that in a 300 nm thick polycrystalline diamond film on a quartz substrate, the SiV centers in the diamond grains possess similar temperature-dependent (13-300 K) PL decay dynamics as the SiV centers in monocrystalline diamond, which suggests that most of the SiV centers are not directly interconnected with the defects of the diamond thin films, i.e. that the carriers excited within the centers do not leak into the defects of the film. The activation energy ΔE = 54 meV and the attempt frequency α = 2.6 were extracted from the measured data. These values corresponded very well with the published values for SiV centers in monocrystalline diamond. We support this claim by measuring the transient absorption via a pump and probe technique, where we separated the nanosecond recombination dynamics of carriers in SiV centers from the picosecond decay dynamics of polycrystalline diamond defects. Our results show that PL emission properties of SiV centers in polycrystalline diamond thin films prepared via chemical vapor deposition are very similar to those in monocrystalline diamond thereby opening the door for their application in diamond photonics and sensing.

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.

Photonic crystal cavity-enhanced emission from silicon vacancy centers in polycrystalline diamond achieved without postfabrication fine-tuning.

Diamond optical centers have recently emerged as promising single-photon sources for quantum photonics. Particularly, negatively charged silicon vacancy (SiV-) centers show great promise due to their narrow zero-phonon emission line present also at room temperature. However, due to fabrication tolerances it is challenging to prepare directly photonic structures with optical modes spectrally matching the emission of SiV- centers. To reach the spectral overlap, photonic structures must typically undergo complicated post-processing treatment. In this work, suspended photonic crystal cavities made of polycrystalline diamond are engineered and more than 2.5-fold enhancement of the SiV- center zero-phonon line intensity via coupling to the cavity photonic mode is demonstrated. The intrinsic non-homogeneous thickness of the diamond thin layer within the sample is taken as an advantage that enables reaching the spectral overlap between the emission from SiV- centers and the cavity modes without any post-processing. Even with lower optical quality compared to monocrystalline diamond, the fabricated photonic structures show comparable efficiency for intensity enhancement. Therefore, the results of this work may open up a promising route for the application of polycrystalline diamond in photonics.

Charge Carrier Injection Electroluminescence with CO-Functionalized Tips on Single Molecular Emitters.

We investigate electroluminescence of single molecular emitters on NaCl on Ag(111) and Au(111) with submolecular resolution in a low-temperature scanning probe microscope with tunneling current, atomic force, and light detection capabilities. The role of the tip state is studied in the photon maps of a prototypical emitter, zinc phthalocyanine (ZnPc), using metal and CO-metal tips. CO-functionalization is found to have an impact on the resolution and contrast of the photon maps due to the localized overlap of the p-orbitals on the tip with the molecular orbitals of the emitter. The possibility of using the same CO-functionalized tip for tip-enhanced photon detection and high resolution atomic force is demonstrated. We study the electroluminescence of ZnPc, induced by charge carrier injection at sufficiently high bias voltages. We propose that the distinct level alignment of the ZnPc frontier orbitals with the Au(111) and Ag(111) Fermi levels governs the primary excitation mechanisms as the injection of electrons and holes from the tip into the molecule, respectively. These findings put forward the importance of the tip status in the photon maps and contribute to a better understanding of the photophysics of organic molecules on surfaces.

Nonequilibrium Dynamics Induced by Scattering Forces for Optically Trapped Nanoparticles in Strongly Inertial Regimes.

The forces acting on optically trapped particles are commonly assumed to be conservative. Nonconservative scattering forces induce toroidal currents in overdamped liquid environments, with negligible effects on position fluctuations. However, their impact in the underdamped regime remains unexplored. Here, we study the effect of nonconservative scattering forces on the underdamped nonlinear dynamics of trapped nanoparticles at various air pressures. These forces induce significant low-frequency position fluctuations along the optical axis and the emergence of toroidal currents in both position and velocity variables. Our experimental and theoretical results provide fundamental insights into the functioning of optical tweezers and a means for investigating nonequilibrium steady states induced by nonconservative forces.

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.

Two-dimensional photonic crystals increasing vertical light emission from Si nanocrystal-rich thin layers.

We have fabricated two-dimensional photonic crystals (PhCs) on the surface of Si nanocrystal-rich SiO2 layers with the goal to maximize the photoluminescence extraction efficiency in the normal direction. The fabricated periodic structures consist of columns ordered into square and hexagonal pattern with lattice constants computed such that the red photoluminescence of Si nanocrystals (SiNCs) could couple to leaky modes of the PhCs and could be efficiently extracted to surrounding air. Samples having different lattice constants and heights of columns were investigated in order to find the configuration with the best performance. Spectral overlap of the leaky modes with the luminescence spectrum of SiNCs was verified experimentally by measuring photonic band diagrams of the leaky modes employing angle-resolved spectroscopy and also theoretically by computing the reflectance spectra. The extraction enhancement within different spatial angles was evaluated by means of micro-photoluminescence spectroscopy. More than 18-fold extraction enhancement was achieved for light propagating in the normal direction and up to 22% increase in overall intensity was obtained at the spatial collection angle of 14°.

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.

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.

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.

A complex study of the fast blue luminescence of oxidized silicon nanocrystals: the role of the core.

Silicon nanocrystals (SiNCs) smaller than 5 nm are a material with strong visible photoluminescence (PL). However, the physical origin of the PL, which, in the case of oxide-passivated SiNCs, is typically composed of a slow-decaying red-orange band (S-band) and of a fast-decaying blue-green band (F-band), is still not fully understood. Here we present a physical interpretation of the F-band origin based on the results of an experimental study, in which we combine temperature (4-296 K), temporally (picosecond resolution) and spectrally resolved luminescence spectroscopy of free-standing oxide-passivated SiNCs. Our complex study shows that the F-band red-shifts only by 35 meV with increasing temperature, which is almost 6 times less than the red-shift of the S-band in a similar temperature range. In addition, the F-band characteristic decay time obtained from a stretched-exponential fit decreases only slightly with increasing temperature. These data strongly suggest that the F-band arises from the core-related quasi-direct radiative recombination governed by slowly thermalizing photoholes.

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.

Effective extraction of photoluminescence from a diamond layer with a photonic crystal.

Diamond-based materials possess many unique properties, one of them being a broad-band visible photoluminescence due to a variety of color centers. However, a high material refractive index makes the extraction of photoluminescence (PL) from a diamond layer inefficient. In this paper, we show that by periodical nanopatterning of the film's surface into a form of two-dimensional photonic crystal, the extraction of PL can be strongly enhanced within the whole visible spectrum compared to the extraction of PL in a pristine or randomly nanopatterned film. On the basis of theoretical calculations, enhancement is shown to be due to the photonic crystal effect, including efficient coupling of an excitation laser into the diamond.