Stable Aqueous Colloidal Solutions of Nd3+: LaF3 Nanoparticles, Promising for Luminescent Bioimaging in the Near-Infrared Spectral Range.

Two series of stable aqueous colloidal solutions of Nd3+: LaF3 single-phase well-crystallized nanoparticles (NPs), possessing a fluorcerite structure with different activator concentrations in each series, were synthesized. A hydrothermal method involving microwave-assisted heating (HTMW) in two Berghof speedwave devices equipped with one magnetron (type I) or two magnetrons (type II) was used. The average sizes of NPs are 15.4 ± 6 nm (type I) and 21 ± 7 nm (type II). Both types of NPs have a size distribution that is well described by a double Gaussian function. The fluorescence kinetics of the 4F3/2 level of the Nd3+ ion for NPs of both types, in contrast to a similar bulk crystal, demonstrates a luminescence quenching associated not only with Nd-Nd self-quenching, but also with an additional Nd-OH quenching. A method has been developed for determining the spontaneous radiative lifetime of the excited state of a dopant ion, with the significant contribution of the luminescence quenching caused by the presence of the impurity OH- acceptors located in the bulk of NPs. The relative quantum yield of fluorescence and the fluorescence brightness of an aqueous colloidal solution of type II NPs with an optimal concentration of Nd3+ are only 2.5 times lower than those of analogous Nd3+: LaF3 single crystals.

Efficient Luminescence Enhancement of Mg2TiO4:Mn4+ Red Phosphor by Incorporating Plasmonic Ag@SiO2 Nanoparticles.

One of prospective ways for boosting efficiency of luminescent materials is their combination with noble metal nanoparticles. Collective, so-called plasmon, oscillations of surface electrons in a nanoparticle can resonantly interact with incident or fluorescent light and cause an increase in the light absorption cross section or radiative rate for an adjacent emitter. Plasmonic inorganic phosphors require gentle host crystallization at which added noble nanoparticles will not suffer from aggregation or oxidation. The prospective plasmonic Mg2TiO4:Mn4+ phosphor containing core@shell Ag@SiO2 nanoparticles is prepared here by spare low-temperature annealing of a sol-gel host precursor. It is revealed that Mn4+ luminescence nonmonotonously depends on the size and concentration of 40 and 70 nm silver nanoparticles. It is demonstrated that luminescence of the Mg2TiO4:Mn4+ phosphor can be up to a 1.5 times increase when Mn4+ excitation is supported by localized surface plasmon resonance in Ag@SiO2 nanoparticles.

White Light Emission and Enhanced Color Stability in a Single-Component Host.

Eu3+ ion can be effectively sensitized by Ce3+ ion through an energy-transfer chain of Ce3+-(Tb3+) n-Eu3+, which has contributed to the development of white light-emitting diodes (WLEDs) as it can favor more efficient red phosphors. However, simply serving for WLEDs as one of the multicomponents, the design of the Ce3+-(Tb3+) n-Eu3+ energy transfer is undoubtedly underused. Theoretically, white light can be achieved with extra blue and green emissions released from Ce3+ and Tb3+. Herein, the design of the white light based on these three multicolor luminescence centers has been realized in GdBO3. It is the first time that white light is generated via accurate controls on the Ce3+-(Tb3+) n-Eu3+ energy transfer in such a widely studied host material. Because the thermal quenching rates of blue, green, and red emissions from Ce3+, Tb3+, and Eu3+, respectively, are well-matched in the host, this novel white light exhibits superior color stability and potential application prospect.

Layered Structure Produced Nonconcentration Quenching in a Novel Eu3+-Doped Phosphor.

Energy migration (energy transfer among identical luminescence centers) is always thought to be related to the concentration quenching in luminescence materials. However, the novel Eu3+-doped Ba6Gd2Ti4O17 phosphor seems to be an exception. In the series of Ba6Gd2(1- x)Ti4O17: xEu3+ ( x = 0.1, 0.3, 0.5, 0.7, and 0.9) phosphors prepared and investigated, no concentration quenching is found. Detailed investigations of the crystal structure and the luminescence properties of Ba6Gd2(1- x)Ti4O17: xEu3+ reveal that the nonoccurrence of concentration quenching is related to the dimensional restriction of energy migration inside the crystal lattices. In Ba6Gd2Ti4O17, directly increasing the number of Eu3+ ions to absorb as much excitation energy as possible allows to achieve a higher brightness. The highly Eu3+-doped Ba6Gd2(1- x)Ti4O17: xEu3+ ( x = 0.9) sample can convert near-UV excitation into red light, whose Commission Internationale de l'Eclairage (CIE) coordinates are (0.64, 0.36) and the color purity can reach up to 94.4%. Moreover, warm white light with the CIE chromaticity coordinates of (0.39, 0.39), the correlated color temperature of 3756 K, and the color rendering index of 82.2 is successfully generated by fabricating this highly Eu3+-doped phosphor in a near-UV light-emitting diode chip together with the green YGAB:Tb3+ and blue BAM:Eu2+ phosphors.

Graphene-Enhanced Raman Scattering from the Adenine Molecules.

An enhanced Raman scattering from a thin layer of adenine molecules deposited on graphene substrate was detected. The value of enhancement depends on the photon energy of the exciting light. The benzene ring in the structure of adenine molecule suggests π-stacking of adenine molecule on top of graphene. So, it is proposed that the enhancement in the adenine Raman signal is explained by the resonance electron transfer from the Fermi level of graphene to the lowest unoccupied molecular orbital (LUMO) level of adenine.

Electro-optics and structural peculiarities of liquid crystal-nanoparticle-polymer composites.

The structural peculiarities and electro-optic performance of liquid crystal (LC)-colloidal nanoparticle (NP)-polymer (P) composites formed by photoinduced phase separation are considered. We classify these materials under two groups according to two limiting cases of polymer morphology. The first group corresponding to small polymer concentration comprises LCs filled with NPs that are stabilized with a polymer network. It is found that, in addition to the light scattering caused by the LC orientational defects, the refractive index mismatch between LC and NP aggregates may significantly affect the electro-optic contrast and its angular characteristics. The second group is represented by polymer dispersed liquid crystals (PDLCs) filled with NPs. It is established that, in the process of photoinduced phase separation of the LC-NP-prepolymer mixture, the nanoparticles are mainly involved with the polymer, serving as building blocks for the polymer matrix. When the aggregation rate of the NPs is high or their size is large, the NPs enhance light scattering in the polymer. For low aggregation rate, NPs modify the effective refractive index and/or the absorption coefficient of the polymer phase without producing any noticeable optical inhomogeneity. Additionally, we found that TiO2 NPs may cause a photochromic effect, which manifests itself in color changes in the course of the photoinduced phase separation. For PDLCs with optically transparent polymer matrices modified by NPs, it is shown that doping with NPs can be used to control the refractive index ratio of the LC and polymer. In this way one can modify the contrast and substantially reduce the off-axis haze of the PDLC. The observed effects show LC-NP-P composites as materials of considerable promise for LCD and other electro-optic applications.

Angular shaping of fluorescence from synthetic opal-based photonic crystal.

Spectral, angular, and temporal distributions of fluorescence as well as specular reflection were investigated for silica-based artificial opals. Periodic arrangement of nanosized silica globules in the opal causes a specific dip in the defect-related fluorescence spectra and a peak in the reflectance spectrum. The spectral position of the dip coincides with the photonic stop band. The latter is dependent on the size of silica globules and the angle of observation. The spectral shape and intensity of defect-related fluorescence can be controlled by variation of detection angle. Fluorescence intensity increases up to two times at the edges of the spectral dip. Partial photobleaching of fluorescence was observed. Photonic origin of the observed effects is discussed.

Gilded nanoparticles for plasmonically enhanced fluorescence in TiO2:Sm3+ sol-gel films.

Silica-gold core-shell nanoparticles were used for plasmonic enhancement of rare earth fluorescence in sol-gel-derived TiO2:Sm3+ films. Local enhancement of Sm3+ fluorescence in the vicinity of separate gilded nanoparticles was revealed by a combination of dark field microscopy and fluorescence spectroscopy techniques. An intensity enhancement of Sm3+ fluorescence varies from 2.5 to 10 times depending on the used direct (visible) or indirect (ultraviolet) excitations. Analysis of fluorescence lifetimes suggests that the locally stronger fluorescence occurs because of higher plasmon-coupled direct absorption of exciting light by the Sm3+ ions or due to plasmon-assisted non-radiative energy transfer from the excitons of TiO2 host to the rare earth ions. PACS: 78; 78.67.-n; 78.67.Bf.

Modification of light absorption in thin CuInS2 films by sprayed Au nanoparticles.

The chemical spray pyrolysis method was used to deposit CuInS2 (CIS) thin films and Au nanoparticles (NPs) in two configurations: glass/Au-NP layer covered with CuInS2 film (Au-NP/CIS) and glass/CuInS2 films covered with Au-NP layer (CIS/Au-NP). According to X-ray diffraction (XRD), the spray of 2 mM HAuCl4 aqueous solution with a volume of 2.5 to 15 ml onto a glass substrate at 340°C results in metallic Au nanoparticles with a similar mean crystallite size in the range of 30 - 38 nm. The mean crystallite sizes remain in the range of 15 - 20 nm when grown onto a CIS film. The prepared films show plasmonic light absorption with increasing intensity in the spectral range of 500- 800 nm when increasing the volume of HAuCl4 solution sprayed. When compared to bare CIS on glass, the absorptance was increased ca. 4.5 times in the case of glass/Au-NP/CIS and ca. 3 times in the case of glass/CIS/Au-NP configuration. The glass/Au-NP/CIS configuration had an advantage since Au-NP could be embedded without chemically damaging the CIS.