Low-temperature time-resolved VUV luminescence spectroscopy of SrF<Subscript>2</Subscript>: Er<Superscript>3+</Superscript> crystals

Time-resolved excitation and emission spectra of SrF₂: Er³⁺ upon selective excitation with synchrotron radiation in the VUV and ultrasoft x-ray ranges at T = 8 K were studied. The VUV luminescence of SrF₂: Er³⁺ derives from high-energy interconfiguration 4f¹⁰5d-4f¹¹ transitions in the Er³⁺ ion. The VUV emission spectrum revealed, in addition to the 164.5-nm band (millisecond-range kinetics), a band at 146.4 nm (with a decay time of less than 600 ps). The formation of excitation spectra for the f-f and f-d transitions in the Er³⁺ ion is discussed.     

Spectra of optical absorption and energy levels diagram of Er<Superscript>3+</Superscript> ions in bulk crystals of aluminum nitride

The absorption spectra of the Er³⁺ ions embedded in the AlN matrix have been investigated. The admixture of erbium was introduced in bulk AlN crystals by diffusion. The absorption lines, which are associated with the intraconfigurational electronic f–f-transitions from the ground ⁴ I _15/2-state to the levels of ion Er³⁺ excited states have been observed in the spectral range of 370–700 nm. The transitions to the state levels ⁴ F _9/2, ² H _11/2, ⁴ F _7/2, ⁴ F _5/2, ² H _9/2, and ⁴ G _11/2 have been investigated in detail at the temperature T = 2 K. The number of the observed lines for these transitions coincides with the theoretically possible one for the electronic f–f-transitions in the ions Er³⁺, which are in the crystal field with the symmetry below cubic. The narrowness of the observed lines and their number convincingly testify the replacement of preferably one regular crystalline position by erbium ions. The implementation of Er³⁺ in the Al³⁺ position with the local symmetry C _3v appears the most probable. The energy positions of the levels of excited states for the investigated transitions have been determined. The diagram of the Er³⁺ ion energy levels in the AlN crystals has been built.     

Scintillation neutron detectors based on <Superscript>6</Superscript>Li-silica glass doped with cerium

The photoluminescence (PL), PL excitation, and PL decay kinetics of ⁶Li₂O-MgO-SiO₂-Ce glasses were studied using time-resolved VUV spectroscopy. The Ce³⁺ ion PL excitation spectrum contains a known group of structural bands at 4.4–5.2 eV caused by 4f → 5d transitions. Moreover, features at 6.4–7.7 eV were detected and their nature is discussed. At an exciting photon energy E_exc > 25 eV, the photon multiplication effect manifests itself. Based on ⁶Li-silica glasses, a scintillation neutron detector with improved parameters was developed and produced.     

Study of absorption spectra of Er<Superscript>3+</Superscript> in KTaO<Subscript>3</Subscript> crystals

The first results of the study of optical absorption spectra of KTaO₃: Er³⁺ crystals are presented. In the 350–660-nm region, lines are observed deriving from intraconfigurational electronic transitions from the ⁴ I _15/2 ground state to levels of the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, ⁴ F _7/2, ⁴ F _5/2(⁴ F _3/2), ² G _9/2, and ⁴ G _11/2 excited states of the Er³⁺ ions. A comprehensive study of transitions to the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, and ⁴ F _7/2 levels at 77 K is carried out. The number of lines observed for the above transitions fits the theoretically possible number for ?-? electronic transitions in Er³⁺ ions in the cubic crystal field. In the case of a differently charged substituted ion, this situation occurs only under nonlocal impurity charge compensation. The energies of the excited state levels for the transitions under study are determined.     

Luminescence characteristics of the Pr<Superscript>3+</Superscript> ion in SrB<Subscript>4</Subscript>O<Subscript>7</Subscript> and SrB<Subscript>6</Subscript>O<Subscript>10</Subscript>

Spectral and kinetic characteristics of the luminescence and luminescence excitation spectra of polycrystalline SrB₄O₇:Pr (1%) and SrB₆O₁₀:Pr (1%) samples are studied at 150–170 K. The samples show an intense luminescence band in the vicinity of 405 nm (¹ S ₀→¹ I ₆ transitions of Pr³⁺) and shorter wavelength bands also assigned to transitions from the ¹ S ₀ level. The main luminescence decay constant is ～2×10^?7 s. The excitation spectra of the ¹ S ₀ luminescence in these crystals are significantly different. The SrB₄O₇:Pr crystal shows three well-resolved bands at 6.14, 6.55, and 6.91 eV in the region of the 4f ²→4f ¹5d transitions and a complex structure in the region of interband transitions (7.1–20 eV), whereas the SrB₆O₁₀:Pr crystal shows a weakly structured band at 6.31 eV and no excitation in the region of the interband transitions. The physical mechanisms that may be responsible for the observed features of the spectra are discussed.     

Isotope shifts in the spectra of LiLuF<Subscript>4</Subscript>:Ho<Superscript>3+</Superscript> crystals due to the isotopic disorder in the lithium sublattice

The isotope shifts of lines in the spectra of the LiLuF₄:Ho³⁺ crystal in the range of the transitions ⁵ I ₈→⁵ I ₇, ⁵ I ₆, and ⁵ I ₅ caused by the isotopic disorder with respect to lithium are measured. The shifts of different lines amount to 0.01–0.036 cm^?1. A comparison with the previously measured isotope shifts in the spectra of the LiYF₄:Ho³⁺ crystal is made.     

Hyperfine magnetic anomaly in isotopic pairs <Superscript>151, 152</Superscript>Eu and <Superscript>152, 153</Superscript>Eu

High-resolution laser spectroscopy measurements of optical hyperfine splitting on the ^{151, 152, 153}Eu isotopes were performed on the atomic transition 4f ⁷6s ^{2 8} S _7/2 → 4f ⁷6s6p ⁶ P _5/2 at λ ≈ 564.58 nm. Values of the nuclear magnetic dipole and electric quadrupole moments are obtained from the measured hyperfine splitting and the magnetic hyperfine anomalies in the isotope pairs ^{151, 152}Eu and ^{152, 153}Eu are deduced. The absolute values of the hyperfine anomaly in both cases are unusually large: 5 (1)%. The possible sources causing these anomalies are discussed.     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

Spectral and luminescence properties of gadolinium gallium garnet epitaxial films doped with terbium

Gadolinium gallium garnet single-crystal films containing terbium are grown through liquid-phase epitaxy from a supercooled solution melt in the PbO-B₂O₃ system. The optical absorption spectra in the wavelength range 0.2–10.0 μm and the luminescence spectra excited by synchrotron radiation with energies in the range 3.5–30.0 eV are investigated at temperatures of 10 and 300 K. It is revealed that the optical absorption spectra contain an absorption band with the maximum at a wavelength λ ≈0.260 μm, which corresponds to the spin-allowed electric dipole transition between the electronic configurations 4f ⁸(⁷ F ₆) → 4f ⁷(⁸ S)5d of the Tb³⁺ ions. The narrow low-intensity absorption bands attributed to the 4f → 4f transitions from the ⁷ F ₆ ground level to the ⁷ F _0–5 multiplet levels of the Tb³⁺ ions are observed in the wavelength range 1.7–10.0 μm. In the luminescence spectra measured at a temperature of 10 K, the highest intensity is observed for a band with the maximum at a wavelength λ ≈ 0.544 μm, which is associated with the ⁵ D ₄ → ⁷ F ₅ radiative transition in the Tb³⁺ ion.     

Divalent rare-earth ions in LaF<Subscript>3</Subscript> crystals

The optical spectra and electric conductivity of LaF₃ crystals doped with 0.01, 0.1, and 0.3 mol % YbF₃, where Yb was partly or completely recharged to the divalent state, are studied. The long-wavelength absorption band of 370 nm is caused by electrons transitioning from state 4f ¹⁴ to the level of anion vacancies. The remaining bands at 300–190 nm are caused by 4f ¹⁴–5d ¹4f ¹³ transitions in Yb²⁺. The bulk electric conductivity and peaks of the dielectric losses of LaF₃–Yb²⁺ crystals are caused by Yb²⁺–anion vacancy dipoles. The activation energy of the reorientation of Yb dipoles is 0.58 eV. The optical and dielectric properties of Yb²⁺ centers are compared to those of Sm²⁺ and Eu²⁺ centers studied earlier in LaF₃ crystals.     

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.     

VUV luminescence of Er<Superscript>3+</Superscript> ions in LiYF<Subscript>4</Subscript> and BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Vacuum ultraviolet luminescence of Er³⁺ ions in LiYF4 and BaY₂F₈ crystals has been investigated. It is revealed that under excitation by 193 nm radiation from an ArF excimer laser the interconfigurational 5d–4f radiative transitions in Er³⁺ ions are observed. It is shown that from the LiYF₄:Er crystal only the spin-forbidden luminescence (λ = 165 nm) is detected, whereas both the spin-forbidden (λ = 169 nm) and spin-allowed (λ = 160.5 nm) components are observed from the BaY₂F₈:Er crystal.     

Ground-State hyperfine structure and nuclear magnetic moment of Thulium-169

The hyperfine structure of the 4f ¹³ 6s ^{2 2} F _7/2 ground state of Tm¹⁶⁹ has been studied with the atomic beam magnetic resonance method. By measuring strongly field-dependent transitions in external magnetic fields between 2200 and 3000 Gauss the interaction between the nuclear magnetic dipole momentμ _I and the external field was determined. These measurements yielded a direct value forμ _I independent of the electronic properties of the Tm-atom. The results are:μ _I=? 0.2310 (15)μ _n (diamagnetically corrected), magnetic dipole interaction constanta=? 374.137661(3) Mc/sec andg _J(4f ¹³ 6s ^{2 2} F _7/2)=1.141189 (3).     

Experimental Study and Analysis of Absorption Spectra of Ni<Superscript>2+</Superscript> Ions in Nickel Orthoborate Ni<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The results of studies of the absorption spectra of nickel orthoborate Ni₃(BO₃)₂ in the range of electronic d–d-transitions are reported. The obtained data are analyzed in the framework of the crystal field theory. The Ni²⁺ ions are located in two crystallographically nonequivalent positions 2a and 4f with point symmetry groups C_2h and C₂, respectively, surrounded by six oxygen ions forming deformed octahedra. The absorption spectra exhibit three intense bands corresponding to spin-resolved transitions from the ground state of nickel ion ³A_2g (³F) to the sublevels of the ³T_2g (³F), ³T_1g (³F) and ³T_1g (³P) triplets split by the spinorbit interaction and the rhombic component of the crystal field. At temperatures below 100 K, the spectra exhibit a thin structure, in which phonon-free lines can be distinguished. Comparison of the calculated frequencies of the zero-phonon transitions with the experimental data allows estimating parameters of the crystal field acting on the nickel ions in the 2a- and 4f-positions, as well as the parameters of electrostatic interaction between the 3d electrons and spin-orbit interaction constants.     

Interrelationship between the polarization moments of different parity upon optical pumping of atoms under the magnetic resonance conditions: I. Experiment on the <Superscript>133</Superscript>Cs and <Superscript>4</Superscript>He atoms

In an experiment with an optical pumping of ¹³³Cs atoms in the 6² S _1/2 ground state, the line shape of the D ^2f magnetic resonance signal for the transverse alignment component oscillating at a double frequency f of a radio-frequency (RF) magnetic field is found to strongly depend on the polarization of pumping radiation. On passage from a linearly polarized pumping light to a circularly polarized (CP) light with a sufficiently strong RF field the ordinary three-peak line with the highest central peak transforms into a two-peak line with a minimum at the center, so that the D ^2f signal line resembles the M ^f signal line of a transverse orientation oscillating at the RF field frequency f. This suggests that the orientation (the first-rank polarization moment (PM)) arising upon CP pumping affects the alignment (the second-rank PM); i.e., the PMs of Cs atoms with different parities of their ranks become coupled. No influence of the polarization of a pumping radiation on the line shape of the D ^2f signal is observed in a similar experiment with the ⁴He atoms in the 2³ S ₁ metastable state.     

Optical 4<Emphasis Type="Italic">f</Emphasis>-4<Emphasis Type="Italic">f</Emphasis> transitions in multiferroic HoMnO<Subscript>3</Subscript>

In the absorption spectra of the hexagonal single-crystal manganite HoMnO₃ in the paramagnetic ferroelectric state, lines near 1.1 and 2.0 μm were observed associated with the transitions ⁵ I ₈ → ⁵ I ₆ and ⁵ I ₈ → ⁵ I ₇, respectively, within the 4f ¹⁰ configuration of the Ho³⁺ ion. At T = 80 K, to the ⁵ I ₈ → ⁵ I ₇ transition corresponds one band at 1.9 μm for both polarizations E ∥ c and E ⊥ c. As the temperature increases from 80 to 293 K, a low-energy band with a peak at 2.04 μm for E ⊥ c and a peak at 2.07 μm for E ∥ c arises associated with transitions from an excited Stark level of the ground ⁵ I ₈ multiplet to the Stark levels of the ⁵ I ₇ multiplet and with an increase in the population of the initial Stark level, the energy of which is ～100 K.     

Spectroscopic study of double sodium-yttrium fluoride crystals doped with erbium Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Er<Superscript>3+</Superscript>: II. Luminescence self-quenching and microparameters and macrorates of energy transfer

Na_0.4Y_0.6F_2.2:Er³⁺ (NYF:Er³⁺) crystals with an Er concentration up to 15% were grown by the Bridgman-Stockbarger method. The luminescence kinetics was investigated for a series of NYF:Er³⁺ crystals (0.5–15% Er), as well as the concentration and temperature quenching of the luminescence from radiative Er levels upon selective laser excitation. It is shown that the luminescence from the ⁴S_3/2 level is quenched significantly with increasing temperature and concentration. The luminescence from the ⁴G_11/2, ²G(H)_9/2, ⁴F_9/2, and ⁴I_9/2 levels is quenched mainly due to nonradiative multiphonon transitions. The concentration quenching of the luminescence from the ⁴I_11/2 and ⁴I_13/2 levels was not observed. Possible schemes of the self-quenching of excited levels of erbium are considered and the microparameters and macrorates of self-quenching are estimated by model quantum-mechanical calculation. Based on the comparison of the calculated and experimental self-quenching rates, the most probable mechanisms and schemes of self-quenching are determined. The self-quenching of the ⁴S_3/2 level of erbium was investigated experimentally and theoretically. Good agreement is obtained between the experimental and the calculated kinetic curves and the dependences of the self-quenching rates on Er concentration. It is concluded that NYF:Er³⁺ crystals are promising as active media for tunable lasers with laser diode pumping.     

Two-step photoconductivity in LiY<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>Lu<Subscript>1 – <Emphasis Type="Italic">x</Emphasis> </Subscript>F<Subscript>4</Subscript>:Ce,Yb crystals

Photoconductivity of LiY_xLu_1–xF₄:Ce,Yb (x = 0–1) crystals is measured under one- and two-step excitation. It is established that the photoconductivity is due to intra-center transitions from excited states of Ce³⁺ ions. The position of the ground 4 f-state of Ce³⁺ ion relative to the bottom of the conduction band is determined. The choice of pumping conditions to obtain the lasing on the 5d–4f transitions of trivalent cerium in these active media is substantiated.     

Intensity parameters for Er<Superscript>3+</Superscript> ions in calcium-niobium-gallium garnet crystals

Based on the analysis of the absorption spectra of Er-doped calcium-niobium-gallium garnet (Er:CNGG) crystals according to the Judd-Ofelt theory, the intensity parameters for these crystals are determined to be Θ₂ = 3.43 × 10^?20 cm² Θ₄ = 1.20 × 10^?20 cm², and Θ₆ = 0.58 × 10^?20 cm². The parameters found are compared with the intensity parameters for other laser oxide crystals. Using these intensity parameters, the probabilities of radiative transitions between the energy levels of Er³⁺ ions in CNGG crystals and the luminescence branching ratios β_JJ’ are calculated. From the measured lifetime of the ⁴ I _11/2 level of Er³⁺ ions (τ = 626 μs) and the probability of the radiative transition from this level (A = 192 s^?1), it is found that about 88% of the excitation energy in the Er:CNGG crystals is nonradiatively transferred from the ⁴ I _11/2 to the ⁴ I _13/2 level. It is suggested that an increase in the oscillator strength and in the line strength of the ⁴ I _15/2 → ² H _11/2 transition of Er³⁺ in CNGG crystals, as well as an increase in the intensity parameter Θ₂ with respect to the corresponding parameters for other garnet crystals are caused by the existence in CNGG crystals of Er³⁺ centers with the environment symmetry lower than D ₂.     

Charge-transfer bands in crystals of alkaline earth fluorides with Eu<Superscript>3+</Superscript> and Yb<Superscript>3 + 1</Superscript>

The absorption, luminescence, and excitation spectra of CaF₂, SrF₂, and BaF₂ crystals with EuF₃ or YbF₃ impurity have been investigated in the range 1–12 eV. In all cases, strong wide absorption bands (denoted as CT₁) were observed at energies below the 4f ⁿ -4f ^{n ? 1}5d absorption threshold of impurity ions. Weaker absorption bands (denoted as CT₂) with energies 1.5–2 eV lower than those of the CT₁ bands have been found in the spectra of CaF₂ and SrF₂ crystals with EuF₃ or YbF₃ impurities. The fine structure of the luminescence spectra of CaF₂ crystals with EuF₃ impurities has been investigated under excitation in the CT bands. Under excitation in the CT₁ band, several Eu centers were observed in the following luminescence spectra: C _4v , O _h , and R aggregates. Excitation in the CT₂ bands revealed luminescence of only C _4v defects.