Near-infrared two-photon excited photoluminescence from Yb3+-doped CsPbClxBr3-x perovskite nanocrystals embedded into amphiphilic silica microspheres.

Nonlinear absorption of metal-halide perovskite nanocrystals (NCs) makes them an ideal candidate for applications which require multiphoton-excited photoluminescence. By doping perovskite NCs with lanthanides, their emission can be extended into the near-infrared (NIR) spectral region. We demonstrate how the combination of Yb3+ doping and bandgap engineering of cesium lead halide perovskite NCs performed by anion exchange (from Cl- to Br-) leads to efficient and tunable emitters that operate under two-photon excitation in the NIR spectral region. By optimizing the anion composition, Yb3+-doped CsPbClxBr3-x NCs exhibited high values of two-photon absorption cross-section reaching 2.3 × 105 GM, and displayed dual-band emission located both in the visible (407-493 nm) and NIR (985 nm). With a view of practical applications of bio-visualisation in the NIR spectral range, these NCs were embedded into silica microspheres which were further wrapped with amphiphilic polymer shells to ensure their water-compatibility. The resulting microspheres with embedded NCs could be easily dispersed in both toluene and water, while still exhibiting a dual-band emission in visible and NIR under both one- and two-photon excitation conditions.

Multifunctional Core/Shell Diamond Nanoparticles Combining Unique Thermal and Light Properties for Future Biological Applications.

We report the development of multifunctional core/shell chemical vapor deposition diamond nanoparticles for the local photoinduced hyperthermia, thermometry, and fluorescent imaging. The diamond core heavily doped with boron is heated due to absorbed laser radiation and in turn heats the shell of a thin transparent diamond layer with embedded negatively charged SiV color centers emitting intense and narrowband zero-phonon lines with a temperature-dependent wavelength near 738 nm. The heating of the core/shell diamond nanoparticle is indicated by the temperature-induced spectral shift in the intensive zero-phonon line of the SiV color centers embedded in the diamond shell. The temperature of the core/shell diamond particles can be precisely manipulated by the power of the incident light. At laser power safe for biological systems, the photoinduced temperature of the core/shell diamond nanoparticles is high enough to be used for hyperthermia therapy and local nanothermometry, while the high zero-phonon line intensity of the SiV color centers allows for the fluorescent imaging of treated areas.

Multi-Frequency Light Sources Based on CVD Diamond Matrices with a Mix of SiV- and GeV- Color Centers and Tungsten Complexes.

Recently, nanodiamonds with negatively charged luminescent color centers based on atoms of the fourth group (SiV-, GeV-) have been proposed for use as biocompatible luminescent markers. Further improvement of the functionality of such systems by expanding the frequencies of the emission can be achieved by the additional formation of luminescent tungsten complexes in the diamond matrix. This paper reports the creation of diamond matrices by a hot filament chemical vapor deposition method, containing combinations of luminescing Si-V and Ge-V color centers and tungsten complexes. The possibility is demonstrated of creating a multicolor light source combining the luminescence of all embedded emitters. The emission properties of tungsten complexes and Si-V and Ge-V color centers in the diamond matrices were investigated, as well as differences in their luminescent properties and electron-phonon interaction at different temperatures.

Duo Emission of CVD Nanodiamonds Doped by SiV and GeV Color Centers: Effects of Growth Conditions.

The investigation of the hot filament chemical vapor deposition nanodiamonds with simultaneously embedded luminescent GeV- and SiV- color centers from solid sources showed that both the absolute and relative intensities of their zero-phonon lines (at 602 and 738 nm) depend on nanodiamond growth conditions (a methane concentration in the CH4/H2 gas mixture, growth temperature, and time). It is shown that a controlled choice of parameters of hot filament chemical vapor deposition synthesis makes it possible to select the optimal synthesis conditions for tailoring bicolor fluorescence nanodiamond labels for imaging biological systems.

Carbon Dots with an Emission in the Near Infrared Produced from Organic Dyes in Porous Silica Microsphere Templates.

Carbon dots (CDs) with an emission in the near infrared spectral region are attractive due to their promising applications in bio-related areas, while their fabrication still remains a challenging task. Herein, we developed a template-assisted method using porous silica microspheres for the formation of CDs with optical transitions in the near infrared. Two organic dyes, Rhodamine 6G and IR1061 with emission in the yellow and near infrared spectral regions, respectively, were used as precursors for CDs. Correlation of morphology and chemical composition with optical properties of obtained CDs revealed the origin of their emission, which is related to the CDs' core optical transitions and dye-derivatives within CDs. By varying annealing temperature, different kinds of optical centers as derivatives of organic dyes are formed in the microsphere's pores. The template-assisted method allows us to synthesize CDs with an emission peaked at 1085 nm and photoluminescence quantum yield of 0.2%, which is the highest value reported so far for CDs emitting at wavelengths longer than 1050 nm.

Effect of Reactive Ion Etching on the Luminescence of GeV Color Centers in CVD Diamond Nanocrystals.

The negatively charged germanium-vacancy GeV- color centers in diamond nanocrystals are solid-state photon emitters suited for quantum information technologies, bio-sensing, and labeling applications. Due to the small Huang-Rhys factor, the GeV--center zero-phonon line emission is expected to be very intensive and spectrally narrow. However, structural defects and the inhomogeneous distribution of local strains in the nanodiamonds result in the essential broadening of the ZPL. Therefore, clarification and elimination of the reasons for the broadening of the GeV- center ZPL is an important problem. We report on the effect of reactive ion etching in oxygen plasma on the structure and luminescence properties of nanodiamonds grown by hot filament chemical vapor deposition. Emission of GeV- color centers ensembles at about 602 nm in as-grown and etched nanodiamonds is probed using micro-photoluminescence and micro-Raman spectroscopy at room and liquid nitrogen temperature. We show that the etching removes the nanodiamond surface sp2-induced defects resulting in a reduction in the broad luminescence background and a narrowing of the diamond Raman band. The zero-phonon luminescence band of the ensemble of the GeV- centers is a superposition of narrow lines originated most likely from the GeV- center sub-ensembles under different uniaxial local strain conditions.

Size Effects in Optical and Magneto-Optical Response of Opal-Cobalt Heterostructures.

Search for new types of efficient magnetoplasmonic structures that combine high transparency with strong magneto-optical (MO) activity is an actual problem. Here, we demonstrate that composite heterostructures based on thin perfectly-arranged opal films and a perforated cobalt nanolayer meet these requirements. Anomalous transmission appears due to periodic perforation of Co consistent with the regular set of voids between opal spheres, while resonantly enhanced MO response involves the effects of surface plasmon-polariton (SPP) excitation at opal/Co interface or those associated with photonic band gap (PBG) in opal photonic crrystals. We observed the enhancement of the MO effect of up to 0.6% in the spectral vicinity of the SPP excitation, and several times less strong effect close to the PBG, while the combined appearance of PBG and SPP decreases the resultant MO response. Observed resonant magneto-optical properties of opal/Co heterostructures show that they can be treated as functional self-assembled magnetoplasmonic crystals with resonantly enhanced and controllable MO effect.

Micro-mesoporous submicron silica particles with pore size tunable in a wide range: synthesis, properties and prospects for LED manufacturing.

An approach has been developed that allows the synthesis of submicron spherical silica particles with a controlled micro-mesoporous structure possessing a large specific surface area (up to 1300 m2g-1). Particle synthesis is carried out by the hydrolysis of a mixture of various organosilanes mostly associated either with CTAB or with each other. A change in the concentration of CTAB in the reaction mixture apparently leads to a change in the formation mechanism of nuclei for the silica particle growth, which allows for varying the diameter of the synthesized particles in the range from 40-450 nm. The effect of the composition of the silica precursor ([3-(methacryloyloxy)propyl]trimethoxysilane, (3-aminopropyl)triethoxysilane and tetraethoxysilane) on the formation process and porosity of the resulting particles is studied. It was shown that by simply varying the ratio of organosilanes in the composition of the precursor, one can control the pore diameter of the particles in a wide range from 0.6-15 nm. The large-pore (up to 15 nm) silica particles are used as a matrix for the spatial distribution of luminescent carbon dots. The incorporation of carbon dots into SiO2particles prevents their aggregation leading to emission quenching after drying, thus allowing us to obtain highly luminescent composite particles. LEDs based on the obtained composite material show bright visible luminescence with spectral characteristics similar to that of a commercial cold white LED.

Strongly Luminescent Composites Based on Carbon Dots Embedded in a Nanoporous Silicate Glass.

Luminescent composites based on entirely non-toxic, environmentally friendly compounds are in high demand for a variety of applications in photonics and optoelectronics. Carbon dots are a recently developed kind of luminescent nanomaterial that is eco-friendly, biocompatible, easy-to-obtain, and inexpensive, with a stable and widely tunable emission. Herein, we introduce luminescent composites based on carbon dots of different chemical compositions and with different functional groups at the surface which were embedded in a nanoporous silicate glass. The structure and optical properties of these composites were comprehensively examined using electron microscopy, Fourier transform infrared transmission, UV-Vis absorption, and steady-state and time-resolved photoluminescence. It is shown that the silicate matrix efficiently preserved, and even enhanced the emission of different kinds of carbon dots tested. The photoluminescence quantum yield of the fabricated nanocomposite materials reached 35-40%, which is comparable to or even exceeds the values for carbon dots in solution.

Enhanced stability of the optical responses from all-inorganic perovskite nanocrystals embedded in a synthetic opal matrix.

Nanostructured luminescent materials based on perovskite nanocrystals (p-NCs) are attractive since their optical properties can be tuned in a wide spectral range with high luminescence quantum yields and lifetimes, however, they lack stability. In this work, the optical properties of highly luminescent colloidal p-NCs (CsPbX3, where X = Cl/Br, Br, I) embedded in porous opal matrices are presented. It is shown that the photoluminescence of the p-NCs embedded into opal matrices possess increased longtime stability of its spectral and kinetic parameters under ambient conditions. LEDs based on the developed materials show pure color p-NC emission with stability of its parameters. The results of this work may expand the knowledge of interactions between luminescent nanoparticles within multicomponent nanostructured materials for further photonic applications.

Controllable spherical aggregation of monodisperse carbon nanodots.

Monodisperse carbon nanodots (MCNDs) having an identical composition, structure, shape and size possess identical chemical and physical properties, making them highly promising for various technical and medical applications. Herein, we report a facile and effective route to obtain monodisperse carbon nanodots 3.5 ± 0.9 nm in size by thermal decomposition of organosilane within the pores of monodisperse mesoporous silica particles with subsequent removal of the silica template. Structural studies demonstrated that the MCNDs we synthesized consist of ∼7-10 defective graphene layers that are misoriented with respect to each other and contain various oxygen-containing functional groups. It was demonstrated that, owing to their identical size and chemical composition, the MCNDs are formed via coagulation primary aggregates ∼10-30 nm in size, which are, in turn, combined into secondary porous spherical aggregates ∼100-200 nm in diameter. The processes of coagulation of MCNDs and peptization of their hierarchical aggregates are fully reversible and can be controlled by varying the MCND concentration or the pH value of the hydrosols. Submicrometer spherical aggregates of MCNDs are not disintegrated as the hydrosol is dried. The thus obtained porous spherical aggregates of MCNDs are promising for drug delivery as a self-disassembling container for medicinal preparations.

Ni-functionalized submicron mesoporous silica particles as a sorbent for metal affinity chromatography.

In this research, a novel IMAC sorbent with high specificity for chlorine-containing compounds was developed. Ni-functionalized monodisperse spherical mesoporous silica particles of 500±25nm diameter were synthesized and their metal affinity properties were studied with the use of diclofenac as the model substance. The particles were aggregatively stable in the pH range of 3-12. The sorbent demonstrated a high adsorption capacity (0.60±0.06µg of DCF per 1mg of the sorbent) and high adsorption/desorption rate (20 and 5min was enough for the sorbent saturation and desorption of DCF, correspondingly). A mixture of eluents with addition of PFOS providing the almost complete recovery (98%) of diclofenac was first proposed. The monodispersity and the high sedimentation and aggregative stability of the particles provide the formation of a stable hydrosol even under ultrasound treatment which makes the mSiO2/Ni particles suitable for batch chromatography.

Low-strain heteroepitaxial nanodiamonds: fabrication and photoluminescence of silicon-vacancy colour centres.

Nanodiamonds with the 'diamond' 1332.5 cm(-1) Raman line as narrow as 1.8 cm(-1) have been produced by reactive ion etching in oxygen plasma of heteroepitaxial diamond particles grown by microwave plasma enhanced chemical vapour deposition (MWPECVD) on silicon. After the etching, a doublet is recorded in the zero-phonon line photoluminescence spectra of an ensemble of silicon-vacancy (SiV) centres at 10 K. Each line of the doublet is split into two lines corresponding to the optical transitions between the split excited and ground energy levels of the SiV centres. These Raman and photoluminescent features have been observed previously only in low-strain homoepitaxial diamond films and single-crystal diamond.

Filtering of elastic waves by opal-based hypersonic crystal.

We report experiments in which high quality silica opal films are used as three-dimensional hypersonic crystals in the 10 GHz range. Controlled sintering of these structures leads to well-defined elastic bonding between the submicrometer-sized silica spheres, due to which a band structure for elastic waves is formed. The sonic crystal properties are studied by injection of a broadband elastic wave packet with a femtosecond laser. Depending on the elastic bonding strength, the band structure separates long-living surface acoustic waves with frequencies in the complete band gap from bulk waves with band frequencies that propagate into the crystal leading to a fast decay.