Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) “soft” luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

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Lanthanide luminescence for functional materials and bio-sciences

Control of spontaneously emitted light lies at the heart of quantum optics. It is essential for diverse applications ranging from miniature lasers and light-emitting diodes, to single-photon sources for quantum information, and to solar energy harvesting. To explore such new quantum optics applications, a suitably tailored dielectric environment is required in which the vacuum fluctuations that control spontaneous emission can be manipulated. Photonic crystals provide such an environment: they strongly modify the vacuum fluctuations, causing the decay of emitted light to be accelerated or slowed down, to reveal unusual statistics, or to be completely inhibited in the ideal case of a photonic bandgap. Here we study spontaneous emission from semiconductor quantum dots embedded in inverse opal photonic crystals. We show that the spectral distribution and time-dependent decay of light emitted from excitons confined in the quantum dots are controlled by the host photonic crystal. Modified emission is observed over large frequency bandwidths of 10%, orders of magnitude larger than reported for resonant optical microcavities. Both inhibited and enhanced decay rates are observed depending on the optical emission frequency, and they are controlled by the crystals’ lattice parameter. Our experimental results provide a basis for all-solid-state dynamic control
of optical quantum systems.

Controlling the dynamics of spontaneous emission from quantum dots by photonic crystals

A review of some properties of chalcogenide glasses and the current status of their applications is given. Techniques to characterize the linear and non-linear properties of these glasses are introduced and used to measure the optical constants of chalcogenide glasses in the form of bulk, thin film and fiber. Different techniques for the fabrication of gratings and waveguides in these glasses are described. Achievable efficiencies of gratings, as well as propagation losses of fabricated waveguides, are presented. The possibilities of fabricating active devices, such as fiber amplifiers and lasers, are presented. Finally, a novel application of chalcogenide glasses, namely all-optical switching for the fabrication of efficient femtosecond switches, is introduced.

Optical properties and applications of chalcogenide glasses: a review

The chemistry of post transition metals is dominated by the group oxidation state N and a lower N-2 oxidation state, which is associated with occupation of a metal s2 lone pair, as found in compounds of Tl(I), Pb(II) and Bi(III). The preference of these cations for non-centrosymmetric coordination environments has previously been rationalised in terms of direct hybridisation of metal s and p valence orbitals, thus lowering the internal electronic energy of the N-2 ion. This explanation in terms of an on-site second-order Jahn–Teller effect remains the contemporary textbook explanation. In this tutorial review, we review recent progress in this area, based on quantum chemical calculations and X-ray spectroscopic measurements. This recent work has led to a revised model, which highlights the important role of covalent interaction with oxygen in mediating lone pair formation for metal oxides. The role of the anion p atomic orbital in chemical bonding is key to explaining why chalcogenides display a weaker preference for structural distortions in comparison to oxides and halides. The underlying chemical interactions are responsible for the unique physicochemical properties of oxides containing lone pairs and, in particular, to their application as photocatalysts (BiVO4), ferroelectrics (PbTiO3), multi-ferroics (BiFeO3) and p-type semiconductors (SnO). The exploration of lone pair systems remains a viable a venue for the design of functional multi-component oxide compounds.

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Stereochemistry of post-transition metal oxides: revision of the classical lone pair model.

Advances in solid state white lighting technologies witness the explosive development of phosphor materials (down-conversion luminescent materials). A large amount of evidence has demonstrated the revolutionary role of the emerging nitride phosphors in producing superior white light-emitting diodes for lighting and display applications. The structural and compositional versatility together with the unique local coordination environments enable nitride materials to have compelling luminescent properties such as abundant emission colors, controllable photoluminescence spectra, high conversion efficiency, and small thermal quenching/degradation. Here, we summarize the state-of-art progress on this novel family of luminescent materials and discuss the topics of materials discovery, crystal chemistry, structure-related luminescence, temperature-dependent luminescence, and spectral tailoring. We also overview different types of nitride phosphors and their applications in solid state lighting, including general ...

Down-Conversion Nitride Materials for Solid State Lighting: Recent Advances and Perspectives.

Ge–Ga–As–S glasses were investigated to develop efficient host materials for the Er 3+ :2.7 μm fiber lasers. Ge30Ga1As9S60 and Ge30Ga2As6S62 (all in at.%) glasses show good thermal stability and high rare-earth solubility up to 0.3 mol%. Mid-infrared emission with a peak wavelength of 2.76 μm and bandwidth of ∼120 nm was observed in Er3+- and Er3+/Tm3+-doped Ge30Ga2As6S62 glasses. Codoping of Tm3+ significantly reduced the lifetime of the Er 3+ : 4 I 13/2 level due to the energy transfer of Er 3+ : 4 I 13/2 → Tm 3+ : 3 F 4 . Thus, the population inversion between the 4 I 11/2 and 4 I 13/2 levels in Er3+ became possible. In Er3+-doped glasses, the rate of cross-relaxation for the 4 I 11/2 level was approximately 11 times faster than that for the 4 I 13/2 level.

Emission properties of the transition in Er3+- and Er3+/Tm3+-doped Ge–Ga–As–S glasses

Phosphor-in-glass (PiG) color converters for LED applications were fabricated with a mixture of phosphors, Y₃Al₅O₁₂:Ce³⁺ (yellow) and CaAlSiN₃:Eu²⁺ (red). The low sintering temperature (550°C) of SiO₂-Na₂O-RO (R=Ba, Zn) glass powder enabled the inclusion of CaAlSiN₃:Eu²⁺ (red) phosphor which cannot be embedded with conventional glass powders for PiGs. By simply varying the mixing ratio of glass to phosphors as well as the ratio of yellow to red phosphors, the facile control of the CIE chromaticity coordinates and correlated color temperature of the LED following the Planckian locus has been achieved. Phosphors were well distributed within the glass matrix without noticeable reactions, preserving the enhanced thermal quenching property of the PiG compared to those with silicone resins, for LEDs.

Control of chromaticity by phosphor in glasses with low temperature sintered silicate glasses for LED applications

16 μm emission originated from Pr3+: (3F3,3F4)→3H4 transition in Pr3+- and Pr3+/Er3+-doped selenide glasses were investigated under an optical pump of a conventional 1480 nm laser diode The measured peak wavelength and full width at half maximum of the fluorescent emission were ∼1650 and >100 nm, respectively A moderate lifetime of the thermally coupled upper manifolds (∼212±5 μs) together with a high stimulated emission cross section of ∼(3±1)×10−20 cm2 promises to be useful for 16 μm band fiber-optic amplifier that can be pumped with an existing high-power laser diode Codoping of Er3+ significantly enhanced the emission intensity by way of a nonradiative Er3+: 4I13/2→Pr3+: (3F3,3F4) energy transfer

1.6 μm emission from Pr3+: (3F3,3F4)→3H4 transition in Pr3+- and Pr3+/Er3+-doped selenide glasses

Conversion to glass-ceramics from glasses made by MSW incinerator fly ash for recycling

Er 2 O 3 -doped PbO-Bi 2 O 3 -Ga 2 O 3 glasses were prepared through the conventional melt-quenching method, and the energy transfer mechanisms in Er 3+ were investigated. The fluorescent emission at 2.73 μm, which is normally quenched in silicate glasses, became evident because of the low phonon energy of PbO-Bi 2 O 3 -Ga 2 O 3 glasses. The measured lifetime of the upper level of 4 I 11/2 was 0.9 ms, and it decreased to ∼0.6 ms with increased Er 3+ concentration. When the concentration of Er 2 O 3 was 0.05 wt%, the coefficient of the cross-relaxation rate for the 4 I 11/2 level was -18 times larger than that of the 4 I 13/2 level. On the other hand, the interaction parameter of energy migration was considerably larger for the 4 I 13/2 level (-52 × 10 -40 cm 6 .s -1 ) compared with the 4 I 11/2 level (-3.1 × 10 -40 cm 6 .s -1 ). Therefore, the major energy transfer mechanism associated with the 4 I 13/2 level was migration induced, whereas that for the 4 I 11/2 level was direct cross relaxation of 4 I 11/2 : 4 I 11/2 → 4 F 7/2 : 4 I 15/2 .

Jong Heo

Papers

Emission properties of the transition in Er3+- and Er3+/Tm3+-doped Ge–Ga–As–S glasses

Control of chromaticity by phosphor in glasses with low temperature sintered silicate glasses for LED applications

1.6 μm emission from Pr3+: (3F3,3F4)→3H4 transition in Pr3+- and Pr3+/Er3+-doped selenide glasses

Conversion to glass-ceramics from glasses made by MSW incinerator fly ash for recycling

Spectroscopic Properties of and Energy Transfer in PbO–Bi2O3–Ga2O3 Glass Doped with Er2O3