Thermal cis–trans isomerization of triazo-benzene

1,3,5-Hydroxy-triazo-benzene (H-TAB) was synthesized through a coupling-oxidation protocol. Temperature-controlled UV, IR, and ab initio calculation were carried out to investigate the cis–trans thermal isomerization of H-TAB. In temperature-controlled UV experiments, λ_max of the π–π¹ band and for the trans conformation at 335 nm and that for the cis form at 282 nm are shifted by increased temperature; band intensities of the π–π¹ transition decrease and λ_max of the π–π¹ band is shifted toward the high-energy region. The maximum peak at 2922 cm⁻¹ is shifted to 2926 cm⁻¹, and that at 2852 cm⁻¹ is shifted to 2856 cm⁻¹ at increased temperature in the temperature-controlled IR experiment. Ab initio calculation reveals that the cis conformation of H-TAB is more stable than the trans form because the cis form has less spatial repulsion. Therefore, the ground-state energy difference induced by steric repulsion of the benzene unit is the driving force of the blue shift in the thermal IR and UV spectra for the triazo-benzene.     

Fast luminescence processes in KI : In caused by excitation in the a absorption band

The temperature dependence of the decay time (τ) of the luminescence pulses from the 440 nm emission band as well as the rise time (τ_R) of luminescence pulses from the 575 nm emission band has been investigated for KI : In by pulsed light excitation in the A absorption band. From the agreement of τ and τ_R independent of the temperature it can be concluded that the X minimum on the ³T₁₄ adiabatic potential energy surface (APES) is mainly populated by a radiationless transition from the tetragonal T minimum of the same APES.Furthermore, a comparison of parameters for the impurity centre luminescence corresponding to the tetragonal emission band in KI : In and KI : Tl has been drawn.     

Emission spectrum of intraband luminescence for single parabolic band under excitation of wide-band-gap insulators by ionizing radiation and particles

Emission spectrum and intensity of picosecond intraband luminescence for single parabolic band approximation of electron conduction band in insulating crystals are calculated. It is shown that the spectral intensity of this intraband emission increases approximately as (?ω)^?1/2 with decrease in photon energy, while the spectral density of photons increases as (?ω)^?3/2. The intensity of this emission is inversely proportional to the longitudinal optical phonon frequency. The total emission yield in this approximation is low, less than 10 photons in the spectral window of silicon photomultipliers per MeV of ionizing particle energy.     

Model for the blue photoluminescence of cadmium sulfide

A model for the blue luminescence of polycrystalline cadmium sulfide and cadmium sulfide single crystals is proposed on the basis of a joint study of the absorption, reflection, emission, and excitation spectra of this luminescence at 77 °K. The blue luminescence arises in the transition of an electron from the conduction band to the 5s^{2 1}S₀ ground level of a super-stoichiometric cadmium atom which has trapped a hole from the valence band. The width of the energy gap (2.614 eV) at κ = 0 is estimated on the basis of the oscillatory nature of the excitation spectrum for the blue luminescence, and the effective mass of heavy holes is estimated.     

Luminescence spectra of lead-doped NaCl,KCl and KBr

The luminescence spectra of lead-doped NaCl, KCl and KBr have been systematically investigated. Special attention has been paid to the effects of concentration and thermal history of the crystals. In the three systems, the emission spectra for A and C band excitation consists mainly of two well-defined emission bands whose energy separation is ～0.7 eV. It has been concluded that none of the bands can be attributed to a single type of lead center but are both typical of Pb²⁺ luminescence. In fact, their behavior can be correlated with that found for most monovalent ions and interpreted in a similar way. The excitation spectra for the two emissions have shown that the A-band is complex. One of the components appearing in very low doped and quenched samples is ascribed to dipoles, whereas additional side bands are attributed to complexes or small aggregates involving Pb²⁺ ions.     

Steady-state fluorescence and photo-isomerization study of 1-methyl-4′-(p-N,N dimethyl-amino styryl) pyridinium iodide

Photochemical and thermal trans/cis isomerization reactions are reported for 1-methyl-4′-(p-N,N dimethyl-amino styryl) pyridinium iodide, Cy, which is synthesized in the trans configuration. In a basic solution the trans form, Cy_tr, cannot isomerise directly to the cis form. Its protonated form, Cy_trH⁺, is active and reacts photochemically from trans to cis isomer, Cy_cH⁺. The quantum yields Φ_tc and Φ_ct are determined in water. Deprotonation process of Cy_cH⁺ yields the cis isomer, Cy_c, which can thermally revert to the stable trans form. The rate constant and the activated parameters of the thermal reaction are also determined. Due to irreversibility of the thermal reaction , a complete molecular reaction cycle is performed in one direction. To get more information on the spectral properties of protonated form, its absorption and fluorescence spectra were investigated in sixteen neat polar protic and aprotic solvents. Absorption energy correlates linearly with hydrogen bond acceptor ability of the solvent. Another linear correlation was found between fluorescence energy of CyH⁺ and free energy for transferring the proton to the surrounding solvent, ΔG_t^o.     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

ESR and conductivity studies of doped polyacetylene

Low temperature ESR spectra of cis-rich and trans-rich polyacetylene, lightly doped with pentafluorides (AsF₅, SbF₅) exhibit two clearly distinguishable ESR lines. Detailed studies of these two lines as a function of temperature, doping concentration and microwave power indicate that one of these lines originates from localized spins, the other from conduction electrons. The concentration of the localized spins, generally speaking, decreases with doping. The Pauli-like susceptibility associated with the conduction electrons changes from 1.5×10^–7 to 15×10^–7 emu·cm³/mole for various doping levels and correlates with the conductivity of the same samples. The longitudinal relaxation time of the localized spins in doped trans-rich was found to beT ₁100 s at low temperatures, consistent with values of others in undoped trans rich. The temperature dependence of the homogeneous transverse relaxationT ₂ of the localized spins in doped trans-rich polyacetylene is similar to that of undoped trans polyacetylene. These facts show that the localized spins originate from undoped regions of the doped polyacetylene, perhaps due to inhomogenous doping. Our results are consistent with either formation of metallic islands, or, probably more, with impurity band conduction in strongly disordered semiconductors.     

Luminescence property studies of α-Al2O3 by means of nanosecond time-resolved VUV spectroscopy

The luminescence spectra of corundum monocrystals grown by different methods are investigated by means of a time-resolved spectroscopy method at temperatures 90 K and 300 K. The existence of fast and slow emission in the VUV luminescence spectra of irradiated and nonirradiated crystals was observed. We observed luminescence bands with a maximum at 326 nm produced by F ⁺ centers. A new type of fast luminescence at the band of 270 nm was found. This is known as cross-luminescence and is connected with the recombination of valence band electrons with the holes in the low ground band. It was shown that the band of 410 nm isn't due to to anionic centers (F-centers), but is determined by the short lifetime center of emission (F ^- -centers). Received 20 October 1998 and Received in final form 20 January 1999     

Nonradiative energy transfer in a concentrated solution of prodan

The temporal characteristics of luminescence decay in concentrated solutions of prodan excited by picosecond laser radiation are studied The electronic spectra exhibit a strong inhomogeneity, which, in the case of elevated solution viscosity, manifests itself under steady-state conditions of measurements. The temporal characteristics of the luminescence decay and the time-resolved luminescence spectra point to the occurrence of relaxation processes causing a long-wavelength shift of the emission band with time. An increase in the prodan concentration from 10^?4 to 5 × 10^?2 M leads to a faster increase in the luminescence lifetime in the long-wavelength spectral region and to a higher rate of shifting of the instantaneous spectra, which is related to energy transfer over the states of inhomogeneous broadening of the luminophore.     

Thermoactivated spectroscopy of heterovalent impurity traps in CdWO4

Abstract

Recombination luminescence emission spectra, TSL and trap spectra estimated by fractional glow technique (FGT), in nominally pure and Li-, Bi- and Ho-doped CdWO₄, crystals are reported. According to the investigations by FGT heterovalent impurities Li, Bi and Ho causes localized electronic states which act as traps for charge carriers. It is shown that TSL results in emission of known blue-green luminescence band by emptying of the Li⁺-related traps in CdWO₄-Li and yellow luminescence band by emptying of the Bi³⁺-related traps in CdWO₄-Bi. It is proposed that blue-green and yellow luminescence occur by recombination correspondingly of free holes and free electrons at different intrinsic tungstate group related luminescence centers.     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

Photoluminescence of Mn doped epitaxial GaAs

We have measured the near band edge photoluminescence of Mn doped liquid phase epitaxially grown GaAs. The photoluminescence spectra at 2°K shows, at low excitation intensities, a structure of up to eight sharp peaks (widths .2 to 1.0 meV) between 1.517 and 1.512 eV, besides the lower energy bands near 1.41 eV due to the deep Mn acceptor level and the usual donor-acceptor bands around 1.47 eV. Attempts to relate the sharp lines to the Mn electronic states, introduced by doping, were unsuccessful. It is our belief that the presence of this particular impurity in our samples allows for whatever states are responsible for the sharp line structure, to reveal themselves in the emission spectrum. A most unespected result is that near band edge sharp line luminescence is observed for impurity concentration as high as 10¹⁸cm^-3.     

Temperature,injection level,and frequency dependences of the luminescence in lightly - and heavily-doped CdTe:In

The temperature dependence, injection level dependence, and modulation frequency response of cathodoluminescence have been measured in Te-rich CdTe:In for materials with In concentrations ranging from 3 × 10¹⁵cm^?3 to 1 × 10¹⁸cm^?3. In lightly-doped material, the 80 K luminescence shows sharp band-edge emission near 1.57 eV and a broad impurity-defect band near 1.4 eV. As temperature increases, the 1.4 eV band quenches out, leaving only the band-edge emission. In heavily-doped material, the band- edge emission is absent and the 80 K luminescence shows only the 1.4 eV band. As the temperature increases from 80 K to 300 K, the 1.4 eV band does not quench out but rather undergoes a complex evolution into a long tail on the band-edge emission which begins to appear at approximately 140 K. At a temperature of 200 K, where the luminescence of the heavily-doped material consists of a broad but structured band approximately 0.2 eV in width, frequency response measurements indicate that band-to-band transitions contribute to the high-energy part of the broad luminescence while the remainder of the band results from slower transitions. The frequency and temperature dependences suggest that the luminescence involves an impurity level that has merged with a band edge at an In concentration of $\text{1 × 10}{}^{18}\text{cm}{}^3$. We interpret this behavior as suggesting that the 1.4 eV luminescence in Te-rich CdTe:In results from a partially-forbidden transition between conduction band and a deep acceptor level rather than from an intracenter type of transition.     

Investigation of luminescence properties in SiO2: Tb,Yb upconversion inverse opal

The SiO₂: Tb, Yb inverse opals with photonic band gap at 465 or 543 nm were prepared, and an effect of photonic band gap on upconversion spontaneous emission from Tb³⁺ was investigated. The results show that the photonic band gap has a significant influence on the upconversion emission of the SiO₂: Tb, Yb inverse opals. The upconversion luminescence of the Tb³⁺ ions is suppressed in the inverse opal compared with the luminescence of that of the reference sample.     

Stmmry talk on evaluation and theory

Abstract

Single crystal samples of Ce³⁺-doped fluorides CaNaYF₆ and BaMgF₄ have been grown in a reducing atmosphere, with the intent of studying the effects of symmetry and ligand coordination on the dopant energy levels. The optical absorption spectra of Ce³⁺ in these crystals consist, at most, of five overlapping bands. The luminescence is also a broad band due to strong electron—phonon interaction in the 5d excited state. The energies of the lowest absorption band and the luminescence band are shifted to low energy compared to those in LiCaAlF₆ and LiYF₄. This trend may be explained by lowering symmetry of the anion-coordinate polyhedra of Ce³⁺ in these crystals.     

Red Mn2+-luminescence in hexagonal aluminates

On UV excitation, a red luminescence band peaking at 690 nm is observed in Eu, Mn doped aluminate lattices containing large trivalent cations and high Mn²⁺-concentrations. The green Mn²⁺ luminescence band occuring at lower Mn²⁺ contents is quenched by the appearance of the red band. The excitation spectra of the red luminescence show that energy transfer takes place from the green Mn²⁺ centres which are located at tetrahedrally surrounded sites to the red emitting Mn²⁺ centres. The last-named are most probably Mn²⁺ ions surrounded octahedrally by oxygen ions. One of these oxygen ions is located at the crystallographic position normally occupied by the large trivalent cation. The dependence of the intensity of the red luminescence on the Mn²⁺ concentration in La-aluminate samples can be explained if it is assumed that the Mn²⁺ ions in tetrahedral sites (the green emitting ones) are all located near the oxygen ions at the large cation sites.     

Luminescence spectroscopy and energy transfer in Eu2+/Mn2+-doped KCaPO4 phosphors

Eu²⁺/Mn²⁺-doped KCaPO₄ phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), SEM, photoluminescence excitation, and emission spectra, and the luminescence decay curves were measured. Mn²⁺ singly doped KCaPO₄ shows the weak origin-red luminescence band peaked at about 590 nm. The Eu²⁺/Mn²⁺ co-doped phosphors emit two distinctive luminescence bands: a blue one centered at 480 nm originating from Eu²⁺ ions and a broad red-emitting one peaked at 590 nm from Mn²⁺ ions. The luminescence intensity from Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ ions. The efficient energy transfer from Eu²⁺ to Mn²⁺ was verified by the photoluminescence spectra together with the luminescence decay curves. The resonance-type energy transfer via a dipole–quadrupole interaction mechanism was supported by the decay lifetimes. The emission colors could be tuned by changing the Mn²⁺-doping concentration.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Ultraviolet excitation of rare-earth-doped YSZ crystals

Abstract

The optical properties of nominally pure and Er³⁺- or Pr³⁺ -doped yttria-stabilized zirconia single crystals were investigated under UV light excitation. In the excitation spectra of both types of doped crystals, a broad UV band is observed. Under excitation with light of different wavelengths inside this band, the luminescence features of the doped crystals are different. YSZ: Pr³⁺ samples exhibit the characteristic 4f → 4f emission of the Pr³⁺ ions. In YSZ: Er³⁺ crystals, both the Er³⁺ ion and the intrinsic luminescence are observed. Host to Er³⁺ ion radiative energy-transfer is also demonstrated. No dependence of the transfer process with the excitation wavelength was found. These results suggest that the UV band in Er³⁺ -doped crystals is associated with the lattice-dopant ion interaction rather than with the 4f5d interconfigurational band of the Er^3? ions.