Dielectric switching in correlation with the structural phase transitions in tetrapropylammonium perchlorate.

The crystals of the tetrapropylammonium perchlorate ([(CH3CH2CH2)4N]ClO4, TePrAClO4) compound undergo two reversible phase transitions: at ca. T1 = 284 K and at ca. T2 = 445 K. The observed phase transitions and distinct dielectric and relaxation effects are due to the dynamic motions of the organic cations and anionic framework. The crystals become ordered at low temperatures, then disordered at room temperature (propyl chains of the organic part as well as perchlorate ions are disordered over the mirror plane at c = 1/4 and 3/4) and highly disordered at high temperatures. The comparable changes in the wavenumber and FWHM shifts (IR and Raman spectroscopy) in the case of tetrapropylammonium and perchlorate ions in the phase transition at T1 and slightly more significant changes for organic cations (juxtaposed with perchlorate ions) in the phase transition at T2 lead to a conclusion that the phase transition at T1 is equally driven by motions of the two ions, while the phase transition at T2 is more influenced by the motions of organic cations. The phase transition at T2 with its large entropy change resembles the behavior found in liquid crystals. The dielectric function values can be switched and tuned in the low- and high-dielectric states, which may indicate the potential application of this material in sensors or actuators.

High-fidelity all-fiber amplification of a gain-switched laser diode.

We demonstrate a multistage erbium fiber amplifier seeded by a gain-switched laser diode operating at a wavelength of 1550 nm and a repetition rate of 1 MHz. The pulse energy is 0.5 µJ, and the pulse duration is 40 ps, resulting in a peak power of 11.4 kW. The three-stage all-fiber amplifier system is designed to avoid any spectral distortions induced by gain saturation or nonlinear effects and high levels of amplified spontaneous emission. The output pulses are close to transform limited with a Gaussian pulse envelope.

Spectroscopy and calculations for 4f(N) → 4f(N-1)5d transitions of lanthanide ions in K3YF6.

In the present work, we report on the combined experimental and theoretical studies of the 4f-5d spectra of Ce(3+), Pr(3+), Nd(3+), Eu(3+), Gd(3+), Tb(3+), Dy(3+), and Er(3+) ions in a newly synthesized K3YF6 matrix. The low temperature experimental 4f-5d excitation spectra have been analyzed and compared with the results of the energy-level and intensity calculations. For this theoretical analysis, the extended phenomenological crystal-field model for the 4f(N-1)5d configuration (i.e., the extended f-shell programs, developed by Prof. M. F. Reid) and exchange charge model (developed by Prof. B. Z. Malkin) have been used together to estimate the crystal field parameters and implement the spectral simulations. On the basis of the results of the performed theoretical analysis, we suggest the most probable positions occupied by optically active ions. Although the spectra of only eight lanthanide ions have been studied, the Hamiltonian parameters of the 4f(N-1)5d configuration have been evaluated for the whole lanthanide series and reported here for the first time, to give a complete and unified description of the spectroscopic properties of the trivalent rare earth ions in the chosen host. In addition to the studies of the 4f-5d transitions, various possible competitive excitation channels overlapping with 4f-5d ones have also been discussed, where a theoretical scheme giving rudiments to understand 4f-6s spectra are proposed for the first time. An excellent agreement between the calculated and measured excitation spectra shapes confirms validity of the performed analysis. The obtained parameters of the crystal field Hamiltonians for different ions and various electron configurations can be used in a straightforward way to generate the energy level positions and calculate the particular transition intensities for any rare earth ion in any particular spectral region. With the aid of the obtained parameters, the positions of the lowest energy levels of the 4f(N), 4f(N-1)5d ,and 4f(N-1)6s configurations of rare earth ions and 4f(N+1)(np)(5) configuration of rare earth ions and ligands (corresponding to the ligand-impurity ion charge transfer transitions) in the band gap of K3YF6 have all been estimated. The obtained Hamiltonian parameters and energy levels diagrams, which include the electronic structure of a host material, can be used as a starting point for analysis of spectroscopic properties of trivalent lanthanides in similar fluorides.

NaYF4:Pr3+ nanocrystals displaying photon cascade emission.

The quantum-cutting process is observed in nanocrystalline fluoride (NaYF(4)) doped with Pr(3+). The thermal decomposition synthesis method was used to synthesize the NaYF(4) nanocrystals with an average size of 42 nm. The morphological high resolution transmission electron microscopy (HRTEM), structural X-ray diffraction (XRD) and spectroscopy, with the use of synchrotron radiation, have been employed to characterize the material. The different excitation energies created different luminescence response of the NaYF(4):Pr(3+) nanocrystals. The quantum-cutting phenomenon has been observed under the direct excitation of the 4f5d bands of praseodymium. After excitation of the NaYF(4) matrix this process is quenched and part of the energy is released through the self-trapped excitons emission. The origin of the different types of emission transitions has been analyzed in detail.

Unusual behavior of Tb3+ in K3YF6 green-emitting phosphor.

We report on photoluminescence studies of Tb3+ in a polycrystalline cryolite type K3YF6 host. The location of the Tb3+ in the center of inversion forbids the electric-dipole transitions of terbium ions in this material. As a consequence almost the entire luminescence intensity is related to the 5D4-(7)F5 magnetic-dipole transition, and it is contained in the extremely narrow spectral bandwidth amounting to 1.7 nm at 8K and to 18 nm at room temperature. The phosphor under study can be efficiently excited making use of intense f-d transitions of Tb3+ in the UV-vacuum-UV region and may be of interest for applications requiring high spectral purity of the emission.