Weak magnetic field behavior of photon echo in a LuLiF4:Er3+ crystal

We report the first observation and study of the photon echo in Er³⁺:LuLiF₄. The energy transition is ⁴ I _15/2 → ⁴ F _9/2 (λ = 6536 Å). The density of ErF₃ is 0.025 wt %. The operation temperature is 1.9 K. Measurements were made at low (up to 1200 Oe) and even zero external magnetic fields. We studied the behavior of the photon echo intensity vs. the magnetic field magnitude and direction about the crystal axis C and vs. the laser pulse separation t ₁₂ and observed an exponential growth and then, after a certain plateau, an exponential decrease in the photon echo intensity as a function of magnetic field upon increasing the magnetic field from zero. The parameters describing the exponential growth and decrease are independent of the direction of magnetic field. The value of the magnetic field (～20–200 Oe) at which the echo intensity is maximal and the value of the maximum itself decrease with increasing pulse separation t ₁₂ and the angle Θ between the magnetic field and crystal axis. The echo intensity decreases exponentially with increasing Θ. The parameter describing the exponential decrease is independent of the magnitude of the field. The echo intensity as a function of pulse separation shows exponential decay. The phase relaxation time depends on the magnitude and direction of the magnetic field. T ₂ is equal to 202 ± 16 ns at zero magnetic field. A phenomenological formula is suggested, which qualitatively presents the mentioned dependences, and the polarization properties of the backward photon echo in this crystal are studied. Because the ion of trivalent erbium is an optimum data carrier, the above results show that fine control of the multichannel transfer of processed optical information may be achieved by weak magnetic fields.     

Oscillations of the photon echo intensity in a pulsed magnetic field: Zeeman splitting in LiLuF<Subscript>4</Subscript>:Er<Superscript>3+</Superscript>

A method of high-resolution time-resolved optical spectroscopy using oscillations of the photon echo intensity in the presence of a perturbation, which splits the optical frequencies of the transitions of two or more ion subgroups, has been proposed and demonstrated. This method has been applied to systems in which the Zee-man effect is manifested. The transition frequencies of ions are switched by a pulsed magnetic field. Oscillations of the photon echo intensity were observed in LiLuF₄:Er³⁺ and LiYF₄:Er³⁺. The first minimum corresponding to the accumulated phase of the electric dipole moment π/2 is reached in the pulsed magnetic field with an amplitude of ～2 G at a duration of 30 ns. The Zeeman splitting in this field is ～10 MHz, which is much less than the laser spectral width (0.15 Å ～ 9 GHz). The g factor of the ⁴ F _9/2(I) excited state of the Er³⁺ ion in the LiLuF₄ matrix has been determined in zero magnetic field. The comparison with the g-factor value found from the measurement of the absorption spectrum in a magnetic field of 8 kG has been performed.     

Effect of the Excitation Radiation Coherence on Oscillations of the Photon Echo Intensity

The physical reasons for observing the splitting of optical lines several orders of magnitude smaller than the spectral width of a laser pulse are investigated. A theory of coherent and incoherent photon echo (PE) in an external static magnetic field and in the presence of a pulsed magnetic field, which causes oscillations of the PE intensity, is elaborated. It is shown that the periods of oscillations in the echo intensity, the echo duration, and the dimensions of the regions in the inhomogeneous line, where the excited ions are coherent, do not depend on the degree of coherence of the laser pulse and on the external static magnetic field. As follows from the theory, in the case of the coherent excitation of the echo, the amplitude of the intensity oscillations is independent of the external static magnetic field if the inhomogeneous line is symmetric. It is shown that the amplitude of the oscillations at the incoherent excitation of the echo is equal to the autocorrelation function of the distribution function of the transition frequency along the inhomogeneous line with the argument equal to the Zeeman splitting of the optical line in the external magnetic field. In this case, the experimental values of the oscillation amplitude are in good agreement with the calculated values of the autocorrelation function for the total inhomogeneous line in LuLiF₄:Er³⁺ (⁴I_15/2?F_9/2 transition). In the same way, the autocorrelation function has been obtained for YLiF₄:Er³⁺ on the same transition.     

Laser excitation of single ion and clustered ion sites in SrF2 : Er3+

Selective laser excitation has been used to study the optical properties of the charge compensated sites in 0.0001%, 0.01%, 0.05% and 0.2% concentrations of SrF₂ : Er³⁺. Using a pulsed, tunable, narrowband dye laser, nine crystallographically inequavalent sites were observed, and the fluorescence and excitation lines associated with each were identified. Concentration dependences, ion pair energy transfer, and crystal field splittings were used to classify these sites as arising from either a single charge compensated Er³⁺ ion or clustered pairs of Er³⁺ ions. At lower concentrations, the four single ion sites dominated the spectra while at higher concentrations the cluster sites weredominant. Several of these sites were found to be similar to sites previously observed in CaF₂ : Er³⁺, and several were correlated to spectra of SrF₂ : Er³⁺ published by other workers.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

Spectral studies of Nd3+ and Er3+ ions in POCl3:SnCl4 laser liquid

The optical absorption spectra of triply ionized neodymium and erbium ions in POCl₃SnCl₄ laser liquid have been studied for the first time in the UV-VIS and NIR regions. Spectroscopic and Judd-Ofelt intensity parameters are evaluated from the observed band positions and their intensities. Radiative lifetimes and the luminescent branching ratios for the excited fluorescent levels of Nd³⁺ and Er³⁺ ions are theoretically estimated and the possible laser transitions are indicated. From the observed splittings of certain bands in the second-derivative spectrum of the Nd³⁺ ion, the crystal field (A ₂₀,A ₄₀) parameters are evaluated assumingC _3h symmetry for the ion.     

From optical spectroscopy to a concentration quenching model and a theoretical approach to laser optimization for Yb3+-doped YLiF4 crystals

A spectroscopic characterization was carried out to identify crystal-field levels for magnetic-dipole transitions of Yb³⁺ ions located in the Y³⁺ dodecahedral S₄ crystallographic site in YLiF₄ (YLF) crystals which were grown either by the Czochralski technique or by the laser heated pedestal growth (LHPG) technique. The concentration dependence of the measured decay time of the ²F_5/2 excited level of Yb³⁺ was analysed in order to understand relevant concentration quenching mechanisms. Under Yb³⁺ ion infrared pumping, self-trapping and up-conversion non-radiative energy transfer to trace rare-earth impurities (Er³⁺, Tm³⁺) has been observed over the visible region and interpreted by a limited-diffusion process within the Yb³⁺ doping ion subsystem to the impurities. The principal parameters useful for a theoretical approach for potential laser applications of Yb³⁺-doped YLiF₄ crystals have also been given.     

Enhancement of up-conversion luminescence in Zn2SiO4:Yb3+, Er3+ by co-doping with Li+ or Bi3+

Yb³⁺/Er³⁺ co-doped Zn₂SiO₄ ceramics are rapidly synthesized by the microwave radiation method. Green and red up-conversion emissions are observed in Zn₂SiO₄: Yb³⁺, Er³⁺ ceramics under 980 nm excitation. The influence of co-doped Li⁺ or Bi³⁺ ion on luminescence intensity for the phosphors has been investigated. At Li⁺ or Bi³⁺ doping concentration of 1 mol%, up-converted green emission can be increased by 6 times and 20 times, respectively. It is believed that co-doped Li⁺ or Bi³⁺ ion results in the local distortion of Er³⁺ in Zn₂SiO₄, increasing the intra-4f transitions of Er³⁺ ions. The local distortion is proved by spectral probing method with Eu³⁺.     

Optical decoherence and persistent spectral hole burning in Er:LiNbO3

Developing new resonant optical materials for spatial-spectral holography and quantum information applications requires detailed knowledge of the decoherence and population relaxation dynamics for the quantum states involved in the optical transitions, motivating the need for fundamental material studies. We report recent progress in studying these properties in erbium-doped lithium niobate at liquid helium temperatures. The influence of temperature, applied magnetic fields, measurement timescale, and dopant concentration were probed using photon echo spectroscopy and time-resolved spectral hole burning on the 1532 nm transition of Er³⁺:LiNbO₃. Effects of spectral diffusion due to interactions between Er³⁺ ions and between the Er³⁺ ion and ⁷Li and ⁹³Nb nuclear spins in the host lattice were observed. In addition, long-lived persistent spectral storage of seconds to minutes was observed due to non-equilibrium population redistribution among superhyperfine states.     

Optical transitions of Pr3+ and Er3+ ions in LiYF4

The optical absorption, emission, and excitation spectra of Pr³⁺ and Er³⁺ ions in LiYF₄ have been measured and energy level schemes established which agree with previous work. The temperature dependence of the emission lifetimes were investigated and analyzed using the Huang-Rhys and Struck-Fonger treatments of multiphonon decay. The non-radiative processes in LiYF₄: Er³⁺ were shown to follow the same “gap law” behavior as Er³⁺ in LaF₃ and MnF₂. Theoretical fits to the Huang-Rhys model allowed the construction of a configuration coordinate diagram for the Er³⁺ system. The non-exponential temperature dependence of the ¹D₂ lifetime in Pr³⁺ can be understood as a non-radiative transition from higher levels.     

The fluorescence properties of Yb3+ and Er3+ Co-doped YAl3(BO3)4 powders prepared by sol-gel method

Yb³⁺ and Er³⁺ co-doped YAB powders were prepared by sol-gel method. The structure and fluorescence properties were investigated. XRD pattern indicated that the single phase was obtained at 1150°C and the structure belonged to rhombohedral. Under 379 nm excitation, two emissions around 983 nm and 1531 nm were observed and the effect of Yb³⁺ ion concentration on the emission intensity was discussed. The energy transfer was observed under 930 nm excitation and the energy transfer efficiencies for all samples were calculated. The lifetimes of ² F _5/2 level of Yb³⁺ ion and ⁴ I _13/2 level of Er³⁺ ion were measured and the effect of Yb³⁺ ion concentration on the lifetime was also discussed. The results indicated that there was an additional mechanism for the decay of ⁴ I _13/2 level in powder samples. The Yb³⁺ and Er³⁺ co-doped YAB powders should be a potential candidate for ceramic laser materials.     

Spin-lattice relaxation and polarization of nuclei in impurity RE3+-YLiF4 single crystals

The temperature dependences of the spin-lattice relaxation of rare-earth ions (RE³⁺) are investigated in YLiF₄ single crystals. The EPR spectra of Er³⁺ and Dy³⁺ are detected and studied at the excited levels of the ground terms. The prospects for RE³⁺-YLiF₄ matrices for the production of polarized targets are shown.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 93–99, September, 1978.     

Investigations of the spin-Hamiltonian parameters for Er3+ ions in AlN crystal

The spin-Hamiltonian parameters (g factor g _//, g _⊥ and hyperfine structure constants A _//, A _⊥) for Er³⁺ ion at the trigonal Al³⁺ site of AlN crystal are calculated by diagonalising the 52 × 52 energy matrix. The matrix are related to the ground mutiplet ⁴I_15/2 and the first to third excited multiplets ⁴I_13/2, ⁴I_11/2 and ⁴I_9/2 for 4f¹¹ ions in trigonal crystal field under an external magnetic field. The crystal-field parameters used in the matrix are obtained from the superposition model and the local lattice relaxation due to the substitution of Er³⁺ for Al³⁺ is considered. The calculated spin-Hamiltonian parameters are in reasonable agreement with the experimental values and the signs of hyperfine structure constants are suggested. The results are discussed.     

Infrared-to-visible frequency upconversion in SrAl2O4 powders containing Er3+ and Yb3+

The phenomenon of frequency upconversion (UC) is observed in Er³⁺:Yb³⁺:SrAl₂O₄ powders prepared by combustion synthesis. Strong UC emission at the green (bands peaked at 521, 538, 547, and 562 nm) and weak UC emission at the red (bands peaked at 659 and 682 nm) corresponding to 4f–4f transitions of Er³⁺ were observed when the samples were irradiated with near-infrared laser excitation at ～980 nm. Saturation of UC emission is observed for concentrations of 1.5 wt.% of Er³⁺ and 1.5 wt.% of Yb³⁺. The green-to-red intensity ratio, on the other hand, increases linearly with Er³⁺ concentration (Er³⁺ concentration varying from 0.5 to 1.5 wt.%) while keeping Yb³⁺ concentration fixed (at 1.5 wt.%). The green UC decay time was measured and Er³⁺–Er³⁺ interaction was suggested as a possible mechanism to explain the luminescence quenching effect observed.     

Photoluminescence of LiNbO3 crystals doped with Er3+ and Yb3+ ions

Results of cooperative phenomena investigations in the impurity subsystem of lithium niobate crystals doped with Er³⁺ and co-doped with Yb³⁺ impurity ions under continuous wave and pulsed excitation at 975 nm and 1064 nm wavelengths are presented. Dependences of some spectroscopic characteristics on the intensity of laser pumping are studied. Based on the pair centers model the analysis of the cooperative luminescence behavior in LiNbO₃:Yb³⁺+Er³⁺ crystals is performed.     

Energy transfer between Yb3+ and Er3+ ions in an Er,Yb:YAl3(BO3)4 crystal

The electron-excitation energy transfer between Er³⁺ and Yb³⁺ ions in Er,Yb:YAl₃(BO₃)₄ crystals has been investigated. Crystals with different concentrations of active ions have been grown, and their luminescence decay kinetics in the spectral range near 1 μm have been experimentally measured. The energy-transfer microparameters have been calculated. It is shown that, to correctly describe the energy transfer in Er,Yb:YAl₃(BO₃)₄ crystals, one must take into account the interactions of higher orders than dipole-dipole interactions.     

Site-selective spectroscopy of Er3+:Ti:LiNbO3 waveguides

Starting from previous investigations in LiNbO₃ bulk crystals, we studied the optical properties of Er³⁺ ions in Ti:LiNbO₃ channel waveguides and investigated the waveguide-specific lattice environment of the Er³⁺ ions (“sites”) caused by the doping method used and the presence of a large number of Ti⁴⁺ ions. For that purpose the method of combined excitation–emission spectroscopy was applied for the first time to waveguides at low temperatures. Comparing the spectroscopic results obtained for the green, red, and near-IR luminescence (λ≈550, ≈650 and ≈980 nm) under direct (450 nm), 2-step (980 nm), and 3-step (1.5 μm) laser excitation, we found several distinguishable Er³⁺ sites which in terms of energy levels and relative numbers are similar to those in bulk material, but exhibit significantly different up-conversion efficiencies and strongly inhomogeneously broadened transitions. Moreover, we were able to distinguish isolated and cluster Er³⁺ sites by their characteristic excitation and emission transition energies and studied the respective excitation/relaxation channels. The cluster sites are most efficient in the up-conversion process, especially under 3-step excitation. Using accepted microscopic models for Er³⁺ and Ti⁴⁺ incorporation into the LiNbO₃ crystal lattice, the site distribution and up-conversion mechanisms are elucidated and their consequences for laser applications in different spectral regions are discussed. Received: 16 November 2000 / Published online: 21 March 2001     

Theoretical studies of the dependence of EPR g-factors on local structure for the trigonal Er3+–VK centres in KMgF3 and KZnF3

The dependence of the EPR g-factors on the local structural parameter for a 4f¹¹ configuration ion Er³⁺ in a trigonal crystal-field has been studied by diagonalizing the 364×364 complete energy matrices. Our studies indicate that the EPR spectra of the trigonal Er³⁺–V_K centers in KMgF₃ and KZnF₃ may be attributed to the translation of the cubic Kramers doublet Γ₇. Furthermore, the EPR g-factors of the trigonal Er³⁺–V_K centers may be interpreted reasonably by the shifts ΔZ≈0.340 Å and ΔZ≈0.303 Å of the Er³⁺ ions toward the charge compensator V_K along the C₃ axis for the KMgF₃:Er³⁺ and the KZnF₃:Er³⁺ systems respectively.     

Photoluminescence characteristics of energy transfer between Er and Bi in Gd2O3: Er, Bi

The phosphors, Bi³⁺- activated Gd₂O₃:Er³⁺, were prepared by sol-gel combustion method, and their photoluminescent properties were investigated under ultraviolet light excitation. The emission spectrum exhibited sharp peaks at about 520, 535, 545, 550 and 559 nm due to (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions. The luminescent intensity was remarkably improved by the incorporation of Bi³⁺ ions under 340 nm light excitation, which suggested very efficient energy transfer from Bi³⁺ ions to Er³⁺ions. The introducing of Bi³⁺ ions broadened the excitation band of the phosphor, of which a new strong peak occurred ranging from 320 to 360 nm due to the 6s²→6s6p transition of Bi³⁺ ions. There is significant energy overlap between the emission band of Bi³⁺ ions and the excitation band of Er³⁺ ions. Under 340 nm light excitation, Bi³⁺ absorbed most of the energy and transferred it to Er³⁺. The energy transfer probability from Bi³⁺ to Er³⁺ is strongly dependent on the Bi³⁺ ion concentration. Also, the sensitization effectiveness was studied and discussed in this paper.