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.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

Luminescence and thermally stimulated recombination processes in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Ce<Superscript>3+</Superscript> crystals

The luminescence and thermally stimulated recombination processes in lithium borate crystals Li₆Gd(BO₃)₃ and Li₆Gd(BO₃)₃:Ce have been studied. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence), temperature dependences of the intensity of steady-state X-ray luminescence (XL), and thermally stimulated luminescence (TSL) spectra of these compounds have been investigated in the temperature range of 90–500 K. The intrinsic-luminescence 312-nm band, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ matrix ions, dominates in the X-ray luminescence spectra of these crystals; in addition, there is a wide complex band at 400–420 nm, which is due to the d → f transitions in Ce³⁺ impurity ions. It is found that the steady-state XL intensity in these bands increases several times upon heating from 100 to 400 K. The possible mechanisms of the observed temperature dependence of the steady-state XL intensity and their correlation with the features of electronic-excitation energy transfer in these crystals are discussed. The main complex TSL peak at 110–160 K and a number of minor peaks, whose composition and structure depend on the crystal type, have been found in all crystals studied. The nature of the shallow traps that are responsible for TSL at temperatures below room temperature and their relation with defects in the lithium cation sublattice are discussed.     

The effect of argon gas pressure on structural,morphological and photoluminescence properties of pulsed laser deposited KY<Subscript>3</Subscript>F<Subscript>10</Subscript>:Ho<Superscript>3+</Superscript> thin films

KY₃F₁₀:Ho³⁺ thin films were deposited by a pulsed laser deposition technique with Nd–YAG laser radiation (λ = 266 nm) on (100) silicon substrate. The XRD and FE-SEM results show improved crystalline structure for the film deposited at a pressure of 1 Torr. The AFM results show that the RMS roughness of the films increases with rise in argon gas pressure. The EDS elemental mapping shows Y-excess for all the films deposited under all pressures, and this is attributed to its higher mass and low volatility as compared to K and F. XPS analysis further confirmed Y-excess in the deposited films. Green PL emission at 540 nm was investigated at three main excitation wavelengths, namely 362, 416 and 454 nm. The PL emission peaks increase with rise in background argon gas pressure for all excitation wavelengths. The highest PL intensity occurred at excitation of 454 nm for all the thin films. In addition, faint red (near infrared) emission was observed at 750 nm for all the excitations. The green emission at 540 nm is ascribed to the ⁵F₄–⁵I₈ and ⁵S₂–⁵I₈ transitions, and the faint red emission at 750 nm is due to the ⁵F₄–⁵I₇ and ⁵S₂–⁵I₇ transitions of Ho³⁺.     

Electronic absorption spectrum of Cs<Subscript>2</Subscript>ZnI<Subscript>4</Subscript> thin films

The absorption spectrum of Cs₂ZnI₄ thin films in the energy range 3–6 eV at temperatures from 90 to 340 K has been investigated. It is established that this compound belongs to direct-gap insulators. Low-frequency exciton excitations are localized in ZnI₄ structural elements of the lattice. Phase transitions at 280 K (paraelectric phase ? incommensurate phase), 135 K (incommensurate phase ? monoclinic ferroelastic phase), and 96 K (monoclinic phase ? triclinic ferroelastic phase) have been found from the temperature dependences of the spectral position and halfwidth of the low-frequency exciton band. Additional broadening of the exciton band is observed for ferroelastic phases; it is likely to be due to exciton scattering from strain fluctuations near domain walls.     

Synthesis and Optical Properties of Novel Red-Emitting PbNb<Subscript>2</Subscript>O<Subscript>6</Subscript>: Eu<Superscript>3+</Superscript> Phosphors

Undoped and PbNb₂O_6:Eu³⁺ (1.0 ≤ x ≤ 6.0 mol%) phosphors were synthesized at 1100 °C for 3.5 h by the conventional solid state reaction method. Synthesized PbNb₂O₆:Eu³⁺ phosphors were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and Photoluminescence (PL) analyses. The PL spectra showed series of excitation peaks between 350 and 430 nm due to the 4f–4f transitions of Eu³⁺. For 395.0 nm excitation, emission spectra of Eu³⁺ doped samples were observed at 591 nm (orange) and 614 nm (red) due to the ⁵D₀ → ⁷F₁ transitions and ⁵D₀ → ⁷F₂ transitions, respectively. PL analysis results also showed that the emission intensity increased by increasing Eu³⁺ ion content. No concentration quenching effect was observed. The CIE chromaticity color coordinates (x,y) of the PbNb₂O₆:Eu³⁺ phosphors were found to be in the red region of the chromaticity diagram.     

Preparation and Photoluminescence of Sm <Superscript>3+</Superscript> Doped YAlO <Subscript>3</Subscript> Phosphor

YAlO₃: Sm³⁺ phosphor has been synthesized by the solid state reaction method with calcium flouride used as a flux. The resulting YAlO₃: Sm³⁺ phosphor was characterized by X-ray diffraction (XRD) technique, Fourier transmission infrared spectroscopy (FTIR), photoluminescence . . PL excitation spectrum was found at 254,332,380,400,407, 603 and 713 nm. Under excitation of UV(713 nm) YAlO₃: Sm³⁺ (0–3 %) broad band emission were observed from 400 to 790 nm with a maximum around 713 nm of YAlO₃ host lattice accompanied by weak emission of Sm³⁺ (⁴G_5/2 – ⁶H_5/2, ⁶H_7/2,⁶H_9/2) transitions. The results of the XRD show that obtained YAlO₃: Sm³⁺ phosphor has a orthorhombic structure. The study suggested that Sm³⁺ doped phosphors are potential luminescence material for laser diode pumping and inorganic scintillators.     

Optical absorption in layered MnGaInS<Subscript>4</Subscript> single crystals

Optical absorption in MnGaInS₄ single crystals has been studied. Direct and indirect optical transitions are found to occur in the range of photon energies of 2.37–2.74 eV and in the temperature range of 83–270 K. The temperature dependence of the band gap has been determined; its temperature coefficients E _gd and E _gi are −5.06 × 10⁻⁴ and −5.35 × 10⁻⁴ eV/K, respectively. MnGaInS4 single crystals exhibit anisotropy in polarized light at the absorption edge; the nature of this anisotropy is explained.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Photoluminescence of CaGa<Subscript>2</Subscript>S<Subscript>4</Subscript>:Pr Polycrystals

The photoluminescence (PL) and PL excitation spectra of CaGa₂S₄ polycrystals doped with praseodymium are studied in the regions of the activator absorption and the fundamental absorption of the host. It is found that the PL excitation spectrum consists of two regions: broadband absorption in the range of 200-380 nm corresponding to the fundamental absorption of the host and the narrow-band absorption of the dopant in the range of 430–515 nm. The luminescence spectra are different for different excitation wave-lengths, which occurs because Pr³⁺ ions substitute divalent cations occupying different crystallographic positions in the host crystal lattice.     

Impurity absorption and luminescence of CuGaSe<Subscript>2</Subscript> crystals

A comparison of the experimental and calculated absorption spectra of CuGaSe₂ crystals revealed the existence of two acceptor levels with ionization energies of 66 and 167 meV in the samples under study. It was found that the luminescence spectra of CuGaSe₂ measured at 77 K exhibit four impurity-band transitions with impurity ionization energies of 66, 99, 136, and 190 meV. An analysis of the temperature dependence of the luminescence intensity in the temperature range 11–77 K revealed a band peaking at 1.671 eV due to the radiation of donor-acceptor pairs. The calculated sum of the ionization energies of the impurities responsible for the formation of donor-acceptor pairs and the temperature dependence of the relative intensities of impurity-band emission were used to determine the ionization energies of the corresponding donor and acceptor.     

Nature of the low-energy excitations of a charge-ordered phase of La<Subscript>0.25</Subscript>Ca<Subscript>0.75</Subscript>MnO<Subscript>3</Subscript> manganites

The nature of the low-energy excitations of polycrystalline and nanostructured La_0.25Ca_0.75MnO₃ samples has been analyzed in order to investigate the mechanisms of charge ordering in manganites. It has been found that the electrodynamic response spectra of La_0.25Ca_0.75MnO₃ in the energy range of 0.5 to 90 meV and the temperature range of 5 to 300 K have no resonance features that could be attributed to the collective excitations of the charge-ordered phase. It has been shown that the absorption lines observed at frequencies of 20–40 and 80–100 cm^–1 are attributed to usual acoustic phonons becoming optically active owing to the structure phase transition and the appearance of a fourfold superstructure with a quadruple period along the crystallographic a axis. The suppression of the superstructure has been revealed in samples with nanocrystallites (≤40 nm). This suppression indicates a relatively weak coupling of the charge and magnetic order parameters with the phonon subsystem.     

Spectroscopic study of thulium-activated double sodium yttrium fluoride Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Tm<Superscript>3+</Superscript> crystals: I. Intensity of spectra and luminescence kinetics

Na_0.4Y_0.6F_2.2:Tm³⁺ crystals with a thulium content from 1 to 100 at % have been grown by the Stockbarger-Bridgman method. The optical spectra of Na_0.4Y_0.6F_2.2:Tm³⁺ crystals were investigated in detail at room and low (10 K) temperatures, and the luminescence kinetics was analyzed using different excitation methods. The structure of the Stark splitting of thulium levels as “quasi-centers,” characterized by inhomogeneous broadening of the Stark components, is determined from analysis of the absorption spectrum at 10 K. The oscillator strengths of the transitions from the ground state to excited multiplets are determined from the absorption cross-section spectra at 300 K for ten transitions in the range 5000–38 500 cm^?1 and seven transitions in the range 5000–28 500 cm^?1. The transition intensity parameters Ω _t , obtained by the Judd-Ofelt method from the spectra due to the transitions to ten and seven excited levels, were found to be, respectively, (i) Ω₂ = 1.89 × 10^?20, Ω₄ = 2.16 × 10^?20, and Ω₆ = 1.40 × 10^?20 cm² and (ii) Ω₂ = 2.04 × 10^?20, Ω₄ = 2.01 × 10^?20, and Ω₆ = 1.44 × 10^?20 cm². These values of the intensity parameters were used to calculate the radiative transition probabilities and branching ratios and to estimate the multiphonon nonradiative transition probabilities for NYF:Tm. The luminescence decay kinetics from thulium radiative levels upon their selective excitation by nanosecond laser pulses has been studied and the lifetimes of thulium radiative levels in NYF crystals have been found.     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

Thermally stimulated recombination processes and luminescence in Li<Subscript>6</Subscript>(Y,Gd,Eu)(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li₆(Y,Gd,Eu)(BO₃)₃ have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃: Eu, and Li₆Gd(BO₃)₃: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the ⁶ P _J → ⁸ S _7/2 transitions in the Gd³⁺ ion and the group of lines at 580–700 nm due to the ⁵ D ₀ → ⁷ F _J transitions (J = 0–4) in the Eu³⁺ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.     

Growth and spectral-luminescent study of SrMoO<Subscript>4</Subscript> crystals doped with Tm<Superscript>3+</Superscript> ions

SrMoO₄ crystals doped with Tm³⁺ ions have been produced from a melt using the Czochralski method; their spectral-luminescent characteristics have been studied, and laser radiation has been generated at the wavelength of 1.94 μm using laser-diode excitation. The high absorption section at the wavelength of 795 nm, the fairly high luminescence section, the long lifetime at the upper laser level ³F4 of 1.5 ms, and a wide luminescence band allow one to hope for developing efficient tunable Tm³⁺: SrMoO₄ crystal lasers with diode pumping in the range of 1.7–2.0 μm, which are capable of implementing SRS self-transformation of radiation into the middle IR band.     

High-energy frenkel cation exciton and specific features of its self-trapping in the CdI<Subscript>2</Subscript>-PbI<Subscript>2</Subscript> crystal system

It has been shown using atomic-force microscopy that the PbI₂ impurity is embedded in the CdI₂ crystal lattice in the form of nanocrystalline inclusions. The model of a high-energy cation exciton related to the ³ P ₂ state of a free Pb²⁺ ion has been considered for the impurity absorption (excitation) band at 3.23 eV. The resonance narrow photoluminescence bands with the split absorption band at 3.12 and 3.20 eV have been compared with the emission of a free Frenkel exciton. It has been demonstrated that, in the temperature range 25–45 K, there arises a self-trapped exciton state, and the main role in its formation is played by the bending vibrations of the CdI₂ crystal lattice. The potential barrier separating the self-trapped state from the free exciton is 23 meV. The photoluminescence band at 2.4 eV is assigned to the emission of the self-trapped high-energy cation exciton of PbI₂ in the CdI₂ crystal lattice.     

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>: I. Intensities of luminescence spectra and kinetics of luminescence

Na_0.4Y_0.6F_2.2:Er³⁺ (NYF:Er) crystals with an erbium concentration as high as 100 at. % (Na_0.4Er_0.6F_2.2) were grown by the Bridgman-Stockbarger method. The optical spectra were investigated at low (6 K) and room temperatures. It is shown that the absorption spectrum of NYF:Er crystals contains wide bands (790–801 and 965–980 nm) corresponding to the emission range of laser diodes. The peak absorption cross section σ_a for the band peaked at λ=970.4 nm is 0.15×10^?20 cm². On the basis of the analysis of the absorption and luminescence spectra at low (6 and 12 K) temperatures, the structure of the Stark splitting of erbium levels was determined as a structure of quasi-centers for which Stark components are inhomogeneously broadened. The oscillator strengths of the transitions from the ground state of erbium to excited multiplets were calculated from the absorption spectra measured at T=300 K, and the intensity parameters Ω_t were determined by the Judd-Ofelt method: Ω₂=1.65×10^?20 cm², Ω₄=0.56× 10^?20 cm², and Ω₆=1.01×10^?20 cm². These values of the intensity parameters were used to calculate the probabilities of radiative transitions and the branching ratios. The rates of multiphonon nonradiative transitions in NYF: Er were estimated. The luminescence decay kinetics for radiative levels of erbium ions upon their selective excitation by nanosecond laser pulses was studied. The intracenter lifetimes of radiative levels of erbium ions were determined from the luminescence kinetics upon selective ion excitation by low-intensity light in a sample with a low erbium concentration (0.5%). It is demonstrated that, with an increase in temperature from 6 to 300 K, luminescence from the ⁴ G _11/2, ² G(H)_9/2, and ⁴ F _9/2 levels is quenched as a result of multiphonon nonradiative transitions. Luminescence from the ⁴ I _9/2 level is quenched only insignificantly with increasing temperature, and no quenching of luminescence from the ⁴ I _11/2 and ⁴ I _13/2 levels is observed. The spectra of steady-state luminescence of NYF:Er(0.5–15%) crystals were investigated upon broadband excitation by UV and UV-visible lamp light and selective time-resolved laser excitation. It is shown that low-lying levels of erbium ions separated by an energy gap smaller than 2500 cm^?1 are populated via cascade mechanisms. On the basis of the results obtained, it is concluded that NYF:Er ³⁺ crystals are promising candidates for active media of tunable diode-pumped lasers.     

Cascade of phase transitions in GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Cascade of phase transitions in GdFe₃(BO₃)₄ at 156, 37, and 9 K has been detected by specific heat measurements and further studied by Raman scattering and Nd³⁺ spectroscopic probe method. A weakly first-order structural phase transition at 156 K is followed by a second-order antiferromagnetic ordering phase transition at 37 K and a first-order spin-reorientational phase transition at 9 K.     

Luminescence properties of transparent ceramics Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Yb

We present the results of studying the luminescence properties of transparent ceramics Y₃Al₅O₁₂:Yb obtained by the vacuum sintering and nanocrystalline technology. In the course of research, we measured the luminescence and luminescence excitation spectra, as well as the temperature and kinetic behavior of luminescence. Our results are analyzed in comparison with the characteristics of corresponding single crystals. We revealed that processes of generation and relaxation of electronic excitations that occur in ceramics, in particular, in the charge transfer state, are similar to processes occurring in crystals. The behavior of two charge-transfer luminescence bands at 340 and 490 nm is studied. In the range 300–600 nm, we revealed a broad emission band of radiation of other type, which is also observed in spectra of undoped ceramics. This broad band is attributed to F⁺ centers. Emission and excitation spectra of charge transfer luminescence at a maximum of the temperature dependence of 100 K are measured for the first time. We found that, upon excitation in the charge transfer band, luminescence in ceramics is more intense than in single crystals with similar concentrations of Yb and has a higher quenching temperature.