Luminescence of yttrium–aluminum garnet crystals with Eu<Superscript>2+</Superscript> impurity ions

Luminescence of yttrium-aluminum garnet Y₃Al₅O₁₂: Eu,Si samples is studied. It is found that luminescence is associated with Eu²⁺ ions, but does not correspond to intracenter 4f ⁶5d ¹–4f ⁷ transitions. Measurements of the excited state lifetime point to the luminescence mechanism involving charge-transfer states.     

Specific features of absorption and luminescence in CsBr: EuOBr crystals

The specific features of the absorption, photoluminescence, x-ray luminescence, thermally stimulated luminescence, and photostimulated luminescence spectra of CsBr: Eu²⁺ single crystals grown using the Bridgman method are investigated in the temperature range 80–500 K at the highest possible dopant content (0.1–0.4 mol % EuOBr in the batch) required for preparing perfect crystals. It is shown that an increase in the dopant content leads to a broadening of the absorption and photoluminescence excitation bands with maxima at wavelengths of 250 and 350 nm due to the interconfigurational transitions 4f⁷(⁸S_7/2) → 4f⁶5d(e _g , t_2g) in Eu²⁺ ions. The photoluminescence and photostimulated luminescence spectra of CsBr: EuOBr single crystals (0.1–0.4 mol % EuOBr) contain a band at a wavelength of λ_max=450 nm and bands at wavelengths of λ_max=508–523 and 436 nm. The last two bands are assigned to Eu²⁺-V_Cs isolated dipole centers and Eu²⁺-containing aggregate centers, respectively. It is revealed that the intensity of the luminescence associated with the aggregate centers (λ_max=508–523 nm) is maximum at an EuOBr content of less than or equal to 0.1 mol % and decreases with an increase in the dopant content. The possibility of forming CsEuBr₃-type nanocrystals that are responsible for the green luminescence observed at a wavelength λ_max=508–523 nm in CsBr: Eu crystals is discussed. The intensity of photostimulated luminescence in the CsBr: EuOBr crystals irradiated with x-ray photons is found to increase as the dopant content increases. It is demonstrated that CsBr: EuOBr crystals at a dopant content in the range 0.3–0.4 mol % can be used as x-ray storage phosphors for visualizing x-ray images with high spatial resolution.     

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.     

Magneto-optical spectroscopy and optical detection of EPR spectra of Yb<Superscript>3+</Superscript> paramagnetic centers with cubic symmetry in single crystals <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Cd,Ca, Pb)

Cubic paramagnetic centers formed by Yb³⁺ impurity ions in fluorite-type crystals MeF₂ (Me = Cd, Ca, Pb) have been investigated using electron paramagnetic resonance, magnetic circular dichroism, magnetic circular polarization of luminescence, Zeeman splitting of optical absorption and luminescence lines, and optical detection of electron paramagnetic resonance. The g factors of the ²Γ₇ state in the excited multiplet ² F _5/2 of Yb³⁺ ions in Me F₂ crystals, the hyperfine interaction constant ¹⁷¹ A (¹⁷¹Yb) for the excited multiplet ² F _5/2 in the CaF₂ crystal, and the energies and symmetry properties of all energy levels of Yb³⁺ ions in MeF₂ crystals are determined. The crystal-field parameters for the crystals under investigation are calculated.     

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.     

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.     

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.     

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.     

Photoluminescence of Ca(Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>S<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript> compounds

Photoluminescence (PL) observed in solid solutions of Ca(Al _x Ga_1–x )₂S₄:Eu²⁺ (x = 0.1–0.3) is studied. It is shown that the increase in emission intensity by 18% is caused by changes in the x values and electronic 5d → 4 f transitions in Eu²⁺ ions. A change in the position of the emission spectrum or its partial shift toward shorter wavelengths is due to an increase in the aluminum concentration and a decrease in the crystal field energy. The energy of the zero phonon line E ₀, redshift D, and the Stokes shift ΔS are determined. A decrease in the photoluminescence intensity maximum and an increase in the half-width of the spectrum are found in the temperature range of 10–300 K. The efficiency of emission at temperatures of 20 and 300 K is almost independent of the excitation power density of up to ~10⁴ W/cm². The luminescence lifetime of Eu²⁺ ions was 383, 357, 346, and 333 ns for x = 0, 0.1, 0.2, and 0.3, respectively.     

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.     

Ionoluminescence of Eu<Superscript>2+</Superscript>–Eu<Superscript>3+</Superscript> clusters in NaF: Eu single crystals

The radiation-impurity modification of NaF: Eu crystals results in the formation of optically active planar heterostructures with a complex set of luminescence centers, including, in particular, clusters of the Eu²⁺–Eu³⁺ type. The luminescence spectra of Eu²⁺–Eu³⁺ centers exhibit bands at wavelengths of 409 and 442 nm, which are associated with Eu²⁺ ions in nonequivalent crystallographic positions, and a band at a wavelength of 610 nm, which is attributed to Eu³⁺ ions. The luminescence spectra of irradiated NaF: Eu samples contain a broad band with a maximum at 506 nm due to the presence of F₂ + F ₊ ³ color centers in the crystal.     

Location of the energy levels of the rare-earth ions in BaF<Subscript>2</Subscript> and CdF<Subscript>2</Subscript>

The location of the energy levels of rare-earth (RE) elements in the energy band diagram of BaF₂ and CdF₂ crystals is determined. The role of RE ³⁺ and RE ²⁺ ions in the capture of charge carriers, luminescence, and the formation of radiation defects is evaluated. It is shown that the substantial difference in the luminescence properties of BaF₂: RE and CdF₂: RE is associated with the location of the excited energy levels in the band diagram of the crystals.     

Spectral-luminescent properties of Eu<Superscript>3+</Superscript> ions in inorganic D<Subscript>2</Subscript>O and POCl<Subscript>3</Subscript>-SnCl<Subscript>4</Subscript> solvents

Absorption and luminescence spectra of Eu³⁺ ions in D₂O and POCl₃-SnCl₄ inorganic solvents were measured. Oscillator strengths and spontaneous radiation transition probabilities for the most intense electron transitions in Eu³⁺ were calculated. Judd-Ofelt parameters, the radiative lifetime of the ⁵ D ₀ metastable level of Eu³⁺ in D₂O-Eu³⁺ and POCl₃-SnCl₄-Eu³⁺ solutions, and matrix elements for radiative transitions from the ⁵ D ₀ level were determined. The luminescence lifetime of the ⁵ D ₀ level of Eu³⁺ in these solutions was measured. The photoluminescence quantum yield for transitions from the ⁵ D ₀ level of Eu³⁺ in ⁵ D ₀ and POCl₃-SnCl₄-Eu³⁺ solutions was found to be 0.32 and 0.88, respectively.     

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.     

Spectroscopy of NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> and NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> crystals as advanced laser materials

Single crystals of double sodium-containing lanthanum and gadolinium molybdates doped with Tm³⁺ ions were synthesized by the Czochralski method. The spectroscopic properties of these crystals were investigated from the viewpoint of their use as active media in diode-pumped lasers. The polarized spectra of absorption on the ³ H ₄ and ³ F ₄ levels and the polarized spectra of luminescence due to the ³ F ₄-³ H ₆ laser transition were recorded, and the lifetimes of the ³ H ₄ and ³ F ₄ excited states of the Tm³⁺ ions were determined. The luminescence cross sections were calculated using the Füchtbauer-Ladenburg formula. The simulation of the decay curve of the ³ H ₄ excited state according to the Golubov-Konobeev-Sakun method revealed that, in the crystals under investigation, the interaction between Tm³⁺ ions predominantly occurs through the dipole-dipole mechanism.     

Radiative transitions to localized Eu states in Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Eu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te solid solutions

Two types of radiative transitions were observed in the low-temperature photoluminescence spectra of Pb_1?x Eu _x Te (0 ≤ x ≤ 0.09) solid solutions: an intense line corresponding to the transitions from the conduction to the valence band and a series (up to 15) of narrow lines corresponding to the transitions from the hybridized conduction band to the split Eu³⁺ levels. The intensity of the discrete lines increases with x, and their energies (and intensities) weakly depend on the temperature. The absorption and emission of the discrete lines are caused by the 4f ⁷(⁸ S _7/2) ? 4f ⁶(⁷ F _J )[L ₆ ^? + 5dt _2g ] transitions.     

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.     

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.     

VUV spectroscopy of Ce<Superscript>3+</Superscript>-doped Na<Subscript>0.4</Subscript>Lu<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript> single crystals

The short-wave transmission spectrum of Na_0.4Lu_0.6F_2.2 with the visible/ultraviolet transmission edge of 8 eV was studied. Absorption spectra of the 4f—5d transitions of the Ce³⁺ ion in the region of 4–8 eV were studied in Ce³⁺-doped Na_0.4Lu_0.6F_2.2 single crystals. Luminescence spectra in the ultraviolet and visible spectral regions, luminescence decay kinetics and reflection and luminescence excitation spectra in the visible/ultraviolet and ultraviolet regions (4–20 eV) were investigated at helium and room temperatures.