Mo6 cluster-based compounds for energy conversion applications: comparative study of photoluminescence and cathodoluminescence.

We report the photoluminescence (PL) and cathodoluminescence (CL) properties of face-capped [Mo6Xi8La6]2- (X = Cl, Br, I; L = organic or inorganic ligands) cluster units. We show that the emission of Mo6 metal atom clusters depends not only on the nature of X and L ligands bound to the cluster and counter-cations, but also on the excitation source. Seven members of the AxMo6Xi8La6 series (A = Cs+, (n-C4H9)4N+, NH4+) were selected to evaluate the influence of counter-cations and ligands on de-excitation mechanisms responsible for multicomponent emission of cluster units. This study evaluates the ageing of each member of the series, which is crucial for further energy conversion applications (photovoltaic, lighting, water splitting, etc.).

Time-gated luminescence bioimaging with new luminescent nanocolloids based on [Mo6I8(C2F5COO)6]2- metal atom clusters.

Bioimaging and cell labeling using red or near infrared phosphors emitting in the "therapeutic window" of biological tissues have recently become some of the most active research fields in modern medical diagnostics. However, because organic and inorganic autofluorophores are omnipresent in nature, very often the background signal from fluorochromes other than targeted probes has to be eliminated. This discrimination could be available using a time-gated luminescence microscopy (TGLM) technique associated with long lifetime phosphorescent nanocomposites. Here, we report new SiO2 nanostructured particle (50 nm in diameter) embedded luminescent nanosized [Mo6I8(C2F5COO)6]2- metal atom clusters (1 nm in diameter), successfully prepared by the microemulsion technique. This combination provides new physical insight and displays red emission in biological based solution under UV-Vis excitation with long lifetimes of around 17 and 84 µs. Moreover, the nanoparticles can be internalized by cancer cells after surface functionalization by transferrin protein and clearly imaged by TGLM under excitation at 365 nm. The nanocomposites have been mainly characterized by scanning and transmission electron microscopies (SEM and HAADF-STEM), UV-Vis and photoluminescence (PL) spectroscopies.

Visible tunable lighting system based on polymer composites embedding ZnO and metallic clusters: from colloids to thin films.

The development of phosphor devices free of heavy metal or rare earth elements is an important issue for environmental reasons and energy efficiency. Different mixtures of ZnO nanocrystals with Cs2Mo6I8(OOC2F5)6 cluster compound (CMIF) dispersed into polyvinylpyrrolidone matrix have been prepared by very simple and low cost solution chemistry. The resulting solutions have been used to fabricate highly transparent and luminescent films by dip coating free of heavy metal or rare earth elements. The luminescence properties of solution and dip-coated films were investigated. The luminescence of such a system is strongly dependent on the ratios between ZnO and CMIF amounts, the excitation wavelength and the nature of the system. By varying these two parameters (ratio and wavelength), a large variety of colors, from blue to red as well as white, can be achieved. In addition, differences in the luminescence properties have been observed between solutions and thin films as well as changes of CMIF emission band maximum wavelength. This may suggest some possible interactions between the different luminophore centers, such as energy transfer or ligands exchange on the Mo6 clusters.

Local analysis of Eu2+ emission in CaAlSiN3.

We have investigated the local luminescence properties of Eu-doped CaAlSiN3 by using low-energy electron beam (e-beam) techniques. The particles yield broad emission centered at 655 nm with a shoulder at higher wavelength under light excitation, and a broad band around 643 nm with a tail at 540 nm under e-beam excitation. Using cathodoluminescence (CL) in a scanning electron microscope (SEM), we have observed small and large particles, which, although with different compositions, exhibit Eu2+-related emissions at 645 and 635 nm, respectively. Local CL measurements reveal that the Eu2+ emission may actually consist of several bands. In addition to the red broad band, regularly spaced sharp peaks have been occasionally observed. These luminescence variations may originate from a variation in the composition inside CaAlSiN3.

On the origin of fine structure in the photoluminescence spectra of the ß-sialon:Eu2+ green phosphor.

The photoluminescence (PL) and PL excitation (PLE) spectra of Si6-z Al z O z N8-z (ß-sialon):Eu2+ phosphors with small z values (z=0.025-0.24) were studied at room temperature and 6 K. The PL and PLE spectra exhibit fine structure with the PL lines being as sharp as 45-55 nm even at room temperature; this fine structure was enhanced by decreasing the z value. These results can be used for expanding the color gamut of liquid crystal displays, particularly in the blue-green region. From low-temperature measurements, the fine PLE structure was ascribed to discrete energy levels of 7FJ states. The 4f65d excited states of Eu2+ are considered to be localized near the 4f orbital. This is because the bonding of Eu2+ with surrounding atoms is ionic rather than covalent. Lattice phonon absorptions were also observed in the PLE spectrum, revealing that the optically active Eu2+ ions are located in the ß-sialon crystal. The PL spectrum of the sample with the smallest z value (0.025) consists of a sharp zero-phonon line and lattice phonon replicas, which results in a sharp and asymmetric spectral shape.

New Deep-Blue-Emitting Ce-Doped A4-mBnC19+2mX29+m (A = Sr, La; B = Li; C = Si, Al; X = O, N; 0 ≤ m ≤ 1; 0 ≤ n ≤ 1) Phosphors for High-Color-Rendering Warm White Light-Emitting Diodes.

A new sialon Eu3.60LiSi13.78Al6.03O6.82N22.59 has been discovered via the single-particle diagnosis approach. Its crystal structure (space group P3m1) was solved and refined from single-crystal X-ray diffraction data. It has the interesting feature of two types of disorder at the Eu2 site: positional disorder (Eu2a/Eu2b) and substitutional disorder with (Si/Al)2(O/N). The structure is generalized to the formula A4-mBnC19+2mX29+m (A = Sr, La, Eu, Ce; B = Li; C = Si, Al; X = O, N; 0 ≤ m ≤ 1; 0 ≤ n ≤ 1), of which Sr3.61LiSi14.27Al5.61O6.19N23.25 (Sr-sialon, m = 0.41, n = 1) and La2.85Sr0.76LiSi14.86Al4.93O2.89N26.51 (LaSr-sialon, m = 0.40, n = 1) are two examples that have been obtained as a single-phase powder. Sr-sialon:Eu and LaSr-sialon:Eu both show blue to yellow emission, depending on the Eu concentration, whereas Sr-sialon:1% Ce shows a deep-blue emission band centered at 422 nm with a full width at half-maximum of 80 nm and an internal quantum efficiency of 80% (λex = 355 nm). The latter phosphor has very good thermal stability of both emission intensity and color. A white light-emitting diode (LED) containing the newly discovered Sr-sialon:5% Ce as the blue phosphor component shows excellent color-rendering indices (Ra = 96 and R12 = 97) with a correlated color temperature of 4255 K. This indicates that Sr-sialon:Ce is a highly promising deep-blue phosphor for illumination grade white LEDs.

Ce-Doped La3Si6.5Al1.5N9.5O5.5, a Rare Highly Efficient Blue-Emitting Phosphor at Short Wavelength toward High Color Rendering White LED Application.

Phase pure nondoped and Ce doped La3Si6.5Al1.5N9.5O5.5 (Al containing La N-phase) samples have been obtained by solid-state reaction synthesis for the first time. 1% Ce-doped La3Si6.5Al1.5N9.5O5.5 phosphor displays a broad excitation band ranging from UV to 410 nm, with a maximum at 355 nm. UV light excitation results in a narrow Ce3+ 5d-4f emission band (fwhm = 68 nm) centered at 418 nm. The emission can be tuned from 417 nm at 0.5% Ce to 450 nm at 50% Ce. A high internal quantum efficiency up to 84% is achieved for a 1% Ce doped sample, which has CIE chromaticity coordinates of x = 0.157 and y = 0.069, close to the NTSC blue standard (x = 0.155; y = 0.070). Compared to La3Si8O4N11:Ce phosphor, the quantum efficiency and thermal stability have been enhanced for La3Si6.5Al1.5N9.5O5.5:Ce phosphor without shifting the emission peak wavelength. La3Si6.5Al1.5N9.5O5.5:Ce shows less thermal quenching than La3Si8O4N11:Ce and no shift or change in the shape of emission spectra with increasing the temperature from 4 to 573 K. These results show that La3Si6.5Al1.5N9.5O5.5:Ce is more efficient than any other (oxy-)nitride phosphor with an emission in the short wavelength blue region (400-450 nm). A white LED was fabricated using the La3Si6.5Al1.5N9.5O5.5:5%Ce as a blue phosphor. The high color rendering index (Ra = 93.2, R9 = 91.4, and R12 = 89.5) obtained shows that the phosphor is a very promising conversion phosphor for white LEDs.

Low-energy Cathodoluminescence for (Oxy)Nitride Phosphors.

Nitride and oxynitride (Sialon) phosphors are good candidates for the ultraviolet and visible emission applications. High performance, good stability and flexibility of their emission properties can be achieved by controlling their composition and dopants. However, a lot of work is still required to improve their properties and to reduce the production cost. A possible approach is to correlate the luminescence properties of the Sialon particles with their local structural and chemical environment in order to optimize their growth parameters and find novel phosphors. For such a purpose, the low-voltage cathodoluminescence (CL) microscopy is a powerful technique. The use of electron as an excitation source allows detecting most of the luminescence centers, revealing their luminescence distribution spatially and in depth, directly comparing CL results with the other electron-based techniques, and investigating the stability of their luminescence properties under stress. Such advantages for phosphors characterization will be highlighted through examples of investigation on several Sialon phosphors by low-energy CL.