Wide band gap oxides, such as ZnO, SnO2 and ZrO2, are functional materials with a wide range of applications in several important technological areas such as those including lighting, transparent electronics, sensors, catalysis and biolabeling. Recently, doping and co-doping of oxides with lanthanides have attracted a strong interest for lighting purposes, especially among them nanophosphors for bioassays. Tailoring the crystalline materials physical properties for such applications often requires a well-controlled incorporation of dopants in the material lattice and a comprehensive understanding of their role in the oxides matrices. These undoped or intentionally doped oxides have band gap energies exceeding 3.3 eV at room temperature and are known to exhibit optically active centers that span from the ultraviolet to the near infrared region. Typically, by using photon energy excitation above the materials band gap, high quality undoped materials display narrow emission lines near the band edge due to free and bound-exciton recombination, as well as shallow donor-acceptor recombination pairs. Additionally, broad emission bands are often observed in these wide band gap hosts, hampering some of the desired physical properties for further applications. Recognizing and understanding the role of the dopant-related defects when deliberately introduced in the oxide hosts, as well as their influence on the samples luminescence properties, constitutes a matter of exploitation by the scientific community worldwide. In this work, we investigate the luminescence properties of undoped and lanthanide doped oxide materials grown by laser assisted techniques. Laser assisted flow deposition (LAFD) and pulse laser ablation in liquids (PLAL) were used for the growth of ZnO, SnO2 and yttria stabilized ZrO2 (YSZ) micro and nanocrystals with different morphologies, respectively. Regarding the YSZ host, trivalent lanthanide ions were optically activated by in-situ doping and co-doping. The influence of the defect energy states on the optical properties of the different undoped and doped metal oxide hosts is investigated under ultraviolet and infrared excitation by means of photoluminescence and photoluminescence excitation.
J. Rodrigues, A. J. Fernandes, D. Mata, Tiago Holz, R. Carvalho, R. Fath Allah, T. Ben, D. Gonzalez, R. Silva, A. da Cunha, M. Correia, L. Alves, K. Lorenz, A. Neves, F. Costa, T. Monteiro
Laser assisted flow deposition (LAFD) is a very high yield method based on a vapor-solid mechanism, allowing
the production of ZnO crystals in a very short time. The LAFD was used in the growth of different morphologies
(nanoparticles, tetrapods and microrods) of ZnO micro/nanocrystals and their microstructural characterization confirms
the excellent crystallinity of the wurtzite structure. The optical properties of the as-grown ZnO crystals investigated by
low temperature photoluminescence (PL) evidence a well-structured near band edge emission (NBE) due to the
recombination of free (FX), surface (SX) and donor bound (D0X) excitons. Among the most representative emission
lines, the 3.31 eV transition was found to occur in the stacking faults-free microrods. The luminescence behavior
observed in H passivated samples suggests a closer relationship between this optical center and the presence of surface
states.
Besides the unintentionally doped micro/nanocrystals, ZnO/Ag and ZnO/carbon nanotubes (CNT) hybrid structures were
processed by LAFD. The former aims at the incorporation of silver as a p-type dopant and the latter envisaging
photovoltaic applications. Silver-related spherical particles were found to be inhomogeneously distributed at the
microrods surface, accumulating at the rods tips and promoting the ZnO nanorods re-nucleation. Despite the fact that
energy dispersive X-ray measurements suggest that a fraction of the silver could be incorporated in the ZnO rods, no new
related luminescence lines or bands were observed when compared with the as-grown samples. For the case of the
ZnO/CNT composites two main approaches were adopted: i) a direct deposition of ZnO particles on the surface of
vertically aligned multi-walled carbon nanotubes (VACNTs) forests without employing any additional catalyst and ii)
new ZnO/CNT hybrids were developed as buckypaper nanocomposites. The use of the LAFD technique in the first
approach preserves the CNTs structure and alignment and avoids the collapse of the VACNTs array, which is a major
advantage of this method. On the other hand, LAFD grown ZnO nanoparticles and tetrapods were used to produce
ZnO/CNT buckypaper nanocomposites. When compared with the as-grown samples the PL spectra of the composites
structures behave differently. For the case of the ZnO/VACNTs no changes on the peak position and spectral shape were
observed. Only an enhancement of the overall luminescence was found to occur. On contrary, for the buckypaper
nanocomposites notable changes on the spectral shape and peak position were observed, likely due to distinct surface
band bending effects for the ZnO nanoparticles and tetrapods embedded in the CNTs.
Wide band gap oxide media including 4fn or 3dn ions attracts a considerable attention in the context of photonics and bio-photonics applications due to the electromagnetic widespread spectral range covered by the intraionic radiative relaxation of the charged lanthanide and transition metal ions. Converting ultraviolet commercial light into visible luminescence continues to raise interest for the solid state light market, justifying the demand for new and efficient phosphors with wide spectrum coverage and improved thermal quenching behavior. New materials and methods have been thoroughly investigated for the desired purposes. In this work, we report on laser processing for the growth of oxides media such as ZrO2, ZnO among other oxide hosts. The transparent crystalline materials in-situ doped with different amounts of lanthanide or transition metal ions are explored in order to enhance the room temperature ions luminescence by pumping the samples with ultraviolet photons. Spectroscopic studies of the undoped and doped oxide hosts were performed using Raman spectroscopy, photoluminescence (PL) and photoluminescence excitation (PLE).
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