Roy Aad

We discuss a recently proposed novel photonic approach for enhancing the fluorescence of extremely thin chemosensing polymer layers. We present theoretical and experimental results demonstrating the concept of gain-assisted waveguided energy transfer (G-WET) on a very thin polymer nanolayer spincoated on an active ZnO thin film. The G-WET approach is shown to result in an 8-fold increase in polymer fluorescence. We then extend the G-WET concept to nanostructured media. The benefits of using active nanostructured substrates on the sensitivity and fluorescence of chemosensing polymers are discussed. Preliminary theoretical results on enlarged sensing surface and photonic band-gap are presented.

A facile and rapid photochemical method for preparing supported silver nanoparticles (Ag-NPs) in a suspension of faujasite type (FAU) zeolite nanocrystals is described. Silver cations are introduced by ion exchange into the zeolite and subsequently irradiated with a Xe−Hg lamp (200 W) in the presence of a photoactive reducing agent (2-hydroxy-2-methylpropiophenone). UV−vis characterization indicates that irradiation time and intensity (I0) influence significantly the amount of silver cations reduced. The full reduction of silver cations takes place after 60 s of a polychromatic irradiation, and a plasmon band of Ag-NPs appears at 380 nm. Transmission electron microscopy combined with theoretical calculation of the plasmon absorbance band using Mie theory shows that the Ag-NPs, stabilized in the micropores and on the external surface of the FAU zeolite nanocrystals, have an almost spheroidal shape with diameters of 0.75 and 1.12 nm, respectively. Ag-NPs, with a homogeneous distribution of size and morphology, embedded in a suspension of FAU zeolites are very stable (∼8 months), even without stabilizers or capping agents.

We propose a new concept for enhancing the fluorescence of ultrathin nanolayers. In this article, we address the issue of efficient absorption of polymer thin films with nanometer characteristics. For many applications, such as sensing, but also for lighting or photovoltaics, devices require the use of nanometer-sized films of a specific polymer or a luminescent nanolayer in general. Usually, most studies are geared toward enhancing the emission of such luminescent films via Bragg mirror-type cavities, for instance, but little attention is paid for optimizing the absorption of the thin films. We show the principle of gain-assisted waveguiding energy transfer (G-WET) by inserting a gain-active layer between an active nanometer-scale layer (a luminescent polymer in our case) and the passive substrate. Efficient absorption via “recycling” of the pumping photons is ensured by the waveguiding effect due to this high-index active layer. To demonstrate the G-WET effect, two kinds of samples were studied. They consist of extremely thin (∼10 nm) polymer nanolayers spin-coated either on quartz, referred as the passive case, or on a ZnO active thin film (∼170 nm, acting as a gain medium) grown on sapphire, referred as the active case. Samples were characterized by room-temperature photoluminescence (PL) spectroscopy under various pumping intensities. Compared to the quartz substrate, the ZnO thin film induces a remarkable enhancement of a factor ∼8 on the fluorescence of the polymer nanolayer. Observations show that, for the passive quartz substrate case, the PL of the spin-coated polymer rapidly saturates, defining a luminescence limit; whereas, with the active ZnO layer, the polymer presents a nonlinear PL intensity surpassing the saturation level. This new photonic system revealed that the polymer luminescence enhancement is the result of both an efficient energy transfer and a geometrical effect ensured by an evanescent coupling of the waveguided ZnO stimulated emission. Although our work discusses the specific organic−inorganic case of fluorescent polymer and ZnO, the GWET concept can be generalized to any hybrid layered sample verifying the necessary energy transfer conditions discussed in this article, thus, demonstrating that this is of a special interest for efficient absorption and efficient recycling of the excitation photons for any nanometer scale fluorescent layer.

We report on efficient ZnO nanocrystal (ZnO-NC) emission in the near-UV region. We show that luminescence from ZnO nanocrystals embedded in a SiO2 matrix can vary significantly as a function of the annealing temperature from 450°C to 700°C. We manage to correlate the emission of the ZnO nanocrystals embedded in SiO2 thin films with transmission electron microscopy images in order to optimize the fabrication process. Emission can be explained using two main contributions, near-band-edge emission (UV range) and defect-related emissions (visible). Both contributions over 500°C are found to be size dependent in intensity due to a decrease of the absorption cross section. For the smallest-size nanocrystals, UV emission can only be accounted for using a blueshifted UV contribution as compared to the ZnO band gap. In order to further optimize the emission properties, we have studied different annealing atmospheres under oxygen and under argon gas. We conclude that a softer annealing temperature at 450°C but with longer annealing time under oxygen is the most preferable scenario in order to improve near-UV emission of the ZnO nanocrystals embedded in an SiO2 matrix.

We report on the efficient room-temperature photoluminescence (PL) quenching of ZnO in the presence of 2,4-dinitrotoluene (DNT) vapor and for concentration as low as 180 ppb. Compared to ZnO thin films, ZnO nanowires exhibit a strong (95%) and fast (41 s) quenching of the PL intensity in the presence of DNTvapor. Assuming that the PL quenching is due to a trapping of the ZnO excitons by adsorbed DNT molecules, Monte-Carlo calculations show that the nanometric dimensions as well as the better crystallographic quality (longer mean free path) of the ZnO nanowires result in an enhanced trapping process at the origin of the improved sensing properties of the nanowires. The results demonstrate the importance of nanostructures in improving the sensitivity of ZnO. The study also reveals the sensing capability of ZnO nanowires and paves the path towards the potential realization of low-cost sub-ppb nitroaromatic derivative sensors.

Zinc oxide (ZnO) epitaxial thin films grown on c-sapphire substrates by pulsed laser deposition were investigated using angle and polarization-resolved photoluminescence spectroscopy. Side-emission spectra differed significantly from surface-emission spectra in exhibiting dominant, narrow, polarization-resolved peaks. These spectral features were attributed to leaky substrate modes in the layers. Observations were first verified using transmission calculations with nonadjustable parameters, which took into account the dispersion, the anisotropy of the ZnO refractive index, and the dependence on film thickness. Results were consistent with Fabry-Perot-like interference being the origin of the distinctive ZnO luminescence observed at grazing incidence angles. A second analysis, based on the source terms method, was used in order to retrieve the bulk emission properties, including the wavelength-dependent quantum yield and the emission anisotropy. While ZnO thin films were considered here, this analysis method can be extended to any luminescent thin film of similar geometry, demonstrating the potential of leaky mode analysis for probing passive and active material properties.

Heteroepitaxial growths of Zn1−xCdxO films were performed on R-oriented sapphire substrates by metal-organic chemical-vapor deposition. The authors carried out secondary ion mass spectrometry analysis, scanning electron microscopy, photoluminescence, and ellipsometric measurements to investigate the incorporation of cadmium in the layers, as well as its influence on the optical properties. Compositions up to 5.5% Cd were obtained, tuning the photoluminescence emission from 3.36 (ZnO) to 3.1 eV and increasing the refractive index at 600 nm from 1.94 to 2.

We present a theoretical study on the impact of a waveguiding active layer on the emission properties of an ultrathin luminescent film. While the study can be generalized to any material, we focus here on a simple layered medium composed of a conjugated polymers (CPs) thin film, a zinc oxide layer (ZnO) and a sapphire substrate. The study spreads throughout variable aspects including the effect of the structure parameters on the CP luminescence and radiation pattern and more specifically the influence of the absorption and emission properties of the active layer. Comparing between the passive and active layer cases, the obtained results show that an enhancement of the CP luminescence of more than 20 times can be obtained by using an optically active waveguiding underlying layer. The results can be explained in terms of photon recycling where the optically active layer acts as a photon reservoir and a secondary light source for the ultrathin film. This general concept is of a special interest for ultratrace chemosensor.