Photonic Crystal Stimuli-Responsive Chromatic Sensors: A Short Review.

Photonic crystals (PhC) are spatially ordered structures with lattice parameters comparable to the wavelength of propagating light. Their geometrical and refractive index features lead to an energy band structure for photons, which may allow or forbid the propagation of electromagnetic waves in a limited frequency range. These unique properties have attracted much attention for both theoretical and applied research. Devices such as high-reflection omnidirectional mirrors, low-loss waveguides, and high- and low-reflection coatings have been demonstrated, and several application areas have been explored, from optical communications and color displays to energy harvest and sensors. In this latter area, photonic crystal fibers (PCF) have proven to be very suitable for the development of highly performing sensors, but one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) PhCs have been successfully employed, too. The working principle of most PhC sensors is based on the fact that any physical phenomenon which affects the periodicity and the refractive index of the PhC structure induces changes in the intensity and spectral characteristics of the reflected, transmitted or diffracted light; thus, optical measurements allow one to sense, for instance, temperature, pressure, strain, chemical parameters, like pH and ionic strength, and the presence of chemical or biological elements. In the present article, after a brief general introduction, we present a review of the state of the art of PhC sensors, with particular reference to our own results in the field of mechanochromic sensors. We believe that PhC sensors based on changes of structural color and mechanochromic effect are able to provide a promising, technologically simple, low-cost platform for further developing devices and functionalities.

Ag-Sensitized Yb3+ Emission in Glass-Ceramics.

Rare earth doped materials play a very important role in the development of many photonic devices, such as optical amplifiers and lasers, frequency converters, solar concentrators, up to quantum information storage devices. Among the rare earth ions, ytterbium is certainly one of the most frequently investigated and employed. The absorption and emission properties of Yb3+ ions are related to transitions between the two energy levels ²F7/2 (ground state) and ²F5/2 (excited state), involving photon energies around 1.26 eV (980 nm). Therefore, Yb3+ cannot directly absorb UV or visible light, and it is often used in combination with other rare earth ions like Pr3+, Tm3+, and Tb3+, which act as energy transfer centres. Nevertheless, even in those co-doped materials, the absorption bandwidth can be limited, and the cross section is small. In this paper, we report a broadband and efficient energy transfer process between Ag dimers/multimers and Yb3+ ions, which results in a strong PL emission around 980 nm under UV light excitation. Silica-zirconia (70% SiO2-30% ZrO2) glass-ceramic films doped by 4 mol.% Yb3+ ions and an additional 5 mol.% of Na2O were prepared by sol-gel synthesis followed by a thermal annealing at 1000 °C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 430 °C to induce the migration and aggregation of the metal. The structural, compositional, and optical properties were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag dimers/multimers, which could have important applications in different fields, such as PV solar cells and light-emitting near-infrared (NIR) devices.

Ultraviolet-to-visible downconversion luminescence in solgel oxyfluoride glass ceramics containing Eu³âº:GdF3 nanocrystals.

GdF3 nanocrystals doped with Eu3+ ions in oxyfluoride glass ceramics were prepared by a solgel method. The structural properties were examined by x-ray diffraction measurements. The effects of gadolinium codoping on europium emission in the prepared solgel glasses and glass ceramics have been studied. The emission bands originating from the 5D0 state of Eu3+ ions are enhanced under excitation of Gd3+ ions by 273 nm line. The electric dipole 5D0→7F2 transitions were dominant in the samples before heat treatment, whereas magnetic dipole 5D0→7F1 transitions had a higher probability in the samples after annealing. The luminescence lifetime for the 5D0 level of Eu3+ ions in the samples after excitation at 273 nm is long lived in comparison to excitation at 393 nm and increased to 190%. Energy transfer from Gd3+ to Eu3+ was observed.

Optical transitions of Eu3+ and Dy3+ ions in lead phosphate glasses.

Lead phosphate glasses containing Eu(3+) and Dy(3+) have been studied. Local structure was verified using Fourier transform (FT)-IR spectroscopy. Emission bands of Eu(3+) and Dy(3+) ions in lead phosphate glasses are observed in the visible spectral range, which correspond to 5D0→7F(J) (J=0,1,2,4) and 4F(9/2)→6H(J/2) (J=15,13,11) transitions, respectively. Shorter luminescence decays from excited states of Eu(3+) and Dy(3+0 are due to the presence of PbO in phosphate glass.

Visible luminescence of dysprosium ions in oxyhalide lead borate glasses.

Visible luminescence of Dy(3+) ions in oxyhalide lead borate glasses was examined. Luminescence spectra show two intense bands at 480 nm and 573 nm due to (4)F(9/2)→(6)H(15/2) (blue) and (4)F(9/2)→(6)H(13/2) (yellow) transitions of Dy(3+). Luminescence decays from (4)F(9/2) state and yellow-to-blue luminescence intensity ratios (Y/B) were analysed with PbX(2) (X=F, Cl) content. An introduction of PbX(2) to the borate glass results in the increasing of (4)F(9/2) lifetime and the decreasing of yellow-to-blue luminescence intensity ratio, which is due to reduction of covalency between Dy(3+) and O(2-)/X(-) ions.