Study of the line intensity in the optical and magnetooptical spectra in holmium-containing paramagnetic garnets

Studies of line intensity in the optical and magneto-optical spectra in the holmium-containing paramagnetic garnet Ho³⁺:YAG were carried out within the visible spectrum at T = 85 K. Detailed investigation of the magnetic circularly polarized luminescence spectra at 85 and 300 K on ⁵S₂ → ⁵I₈ emission transition in Ho³⁺:YAG was carried out. A quasi-doublet state in the energy spectrum of the Ho³⁺ ions was observed, characterized by a significant magneto-optical activity, which is caused by a large Zeeman splitting of the quasi-doublet. The measurement of the magnetic circular polarized luminescence spectrum carried out within one of the emission lines of the luminescence band ⁵S₂ → ⁵I₈ in Ho³⁺:YAG at 85 K shows significant magneto-optical effects of the intensity change of the emitted light, compared to that measured for the other emission lines in the same luminescent band.     

Comparative study of the luminescence of Al2O3:Ti and Al2O3 crystals under VUV synchrotron radiation excitation

The comparative study of the luminescent properties of Al₂O₃:Ti crystal in comparison with those for undoped Al₂O₃ crystal counterpart is performed under synchrotron radiation excitation with an energy of 3.7–25 eV. Apart from the main emission band peaked at 725 nm related to the ²E → ²T₂ radiative transitions of Ti³⁺ ions, the luminescence of excitons localized around Ti ions in the band peaked at 290 nm and the luminescence of F⁺–Ti and F–Ti centers in the bands peaked at 325 and 434 nm are also found in the emission spectra of Al₂O₃:Ti crystal. We show also that the luminescence of Ti³⁺ ions in Al₂O₃:Ti crystal can be effectively excited by the luminescence of excitons localized around Ti dopant as well as by the luminescence of F–Ti centers.     

Structural and photophysical properties of lanthanide complexes with N-(diphenylphosphoryl)-4-methylbenzenesulfonamide

Lanthanide complexes with N-(diphenylphosphoryl)-4-methylbenzenesulfonamide (HPMSP) as new sensitizers of visible luminescence were obtained. The series of stable lanthanide complexes Na[Ln(PMSP)₄], where Ln = Eu³⁺, Gd³⁺, Tb³⁺ were characterized by X-ray diffraction, IR, absorption, emission, and excitation spectra at 295 and 77 K as well as luminescence decay times and intrinsic emission quantum yields. The Tb complex, exhibiting relatively efficient ligand-to-metal energy transfer and strong metal-centred emission, is a promising candidate for effective UV-to-visible energy converters. Temperature dependent quenching of sensitized ⁵D₀ europium emission and presence of ⁵D₁ emission are discussed.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

Single crystal growth,structure and properties of TlHgBr3

High-quality inclusion-free single crystals of ternary thallium mercury bromide, TlHgBr₃, were successfully grown by Bridgman–Stockbarger method. For the pristine surface of the TlHgBr₃ single crystal, X-ray photoelectron core-level and valence-band spectra were measured. The comparison on a common energy scale of the X-ray photoelectron valence-band spectrum of TlHgBr₃ and the X-ray emission Br Kβ₂ band, representing peculiarities of the energy distribution of the Br 4p states revealed that the main contribution of the valence Br p states, occurred in the upper portion of the valence band, with also their significant contributions in other valence band regions. It has been determined that TlHgBr₃ is a semiconductor with the bandgap energy value of E_g = 2.51 eV at 100 K. The E_g value decreased up to 2.44 eV when temperature increased to 300 K.     

Photoluminescent properties of LiInO2 nanocrystals

Synthesis and luminescence properties of LiInO₂ nanocrystals by the sol–gel process were investigated. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectroscopy and absorption spectra. The well-crystallized tetragonal LiInO₂ can be obtained by heat treatment above 600 °C from XRD. The excitation wavelengths at about 246 nm were associated with charge transfer between In and O with In³⁺ ions in octahedral coordination. The PL spectra excited at 246 nm have a broad and strong emission band maximum at 391 nm, corresponding to the self-activated luminescence. The optical absorption spectra of the 600 °C sample exhibited the band gap energies of 3.7 eV.     

Structure and optical properties of Li2Ga2GeS6 nonlinear crystal

Structure and optical properties of new nonlinear crystal – Li₂Ga₂GeS₆ single crystal of optical quality, grown by the Bridgman technique were studied. The data on transmission, Raman scattering, luminescence emission, excitation and thermal quenching as well as thermostimulated luminescence are presented. Fundamental absorption edge is determined by the direct allowed electronic transitions: The values of optical band gap are estimated. Absorption band at 8.0 μm is due to S–S vibrations. Features in photoluminescence spectra are associated with excitons: both free (narrow line at 371 nm) and self-trapped ones (broad bands at 596, 730 and 906 nm). Spontaneous emission in the 80–170 K range, both at crystal heating and cooling, is typical of pyroelectrics: This confirms the absence of symmetry center in Li₂Ga₂GeS₆ and an opportunity of laser frequency nonlinear conversion.     

SrHfO3-based phosphors and scintillators

The heavily Ce-doped SrHfO₃ (SHO) and the undoped non-stoichiometric SHO sample sets were prepared by solid state reaction in powder form and their luminescence spectra and decay kinetics were measured. Concentration quenching effects and thermally induced ionization of the Ce³⁺ excited states were followed and discussed in the former sample set. In the latter one new emission band at about 334 nm was found in Sr-deficient samples and temperature dependences of its emission intensity and decay times were studied in the detail. Room temperature decay time of about 180 ns and efficient and fast energy transfer from the host to the center of the 334 nm emission make this material promising candidate for X-ray phosphors.     

Ag nanoparticles enhanced near-IR emission from Er3+ ions doped glasses

Vitreous materials containing rare-earth (RE) ions and metallic nanoparticles (NPs) attract considerable interest because the presence of the NPs may lead to an intensification of luminescence. In this work, the characteristics of 1.54 μm luminescence for the Er³⁺ ions doped bismuthate glasses containing Ag NPs were studied under 980 nm excitation. The surface plasmon resonance (SPR) band of Ag NPs appears from 500 to 1500 nm. Transmission electron microscopic (TEM) image reveals that the Ag NPs are dispersed homogeneously with the size from 2 to 7 nm. The strength parameters Ω_t(t = 2, 4, 6), spontaneous emission probability (A), radiative lifetime (τ) and stimulated emission section (σ_em) of Er³⁺ ions were calculated by the Judd–Ofelt theory. When the glass contains 0.2 wt% AgCl, the 1.54 μm fluorescence intensity of Er³⁺ reaches a maximum value, which is 7.2 times higher than that of glass without Ag NPs. The Ag NPs embedded glasses show significantly fluorescence enhancement of Er³⁺ ions by local field enhancement from SPR.     

Spectroscopic investigations on Eu3+ ions in Li–K–Zn fluorotellurite glasses

Eu³⁺ ions incorporated Li–K–Zn fluorotellurite glasses, (70 − x)TeO₂ + 10Li₂O + 10K₂O + 10ZnF₂ + xEu₂O₃, (0 ⩽ x ⩽ 2 mol%) were prepared via melt quenching technique. Optical absorption from ⁷F₀ and ⁷F₁ levels of the Eu³⁺-doped glass has been studied to examine the covalent bonding characteristics, energy band gap and Judd–Ofelt intensity parameters. The emission spectra (⁵D₀ → ⁷F_0,1,2,3,4) of the glasses were used to estimate the luminescence enhancement, asymmetric environment in the vicinity of Eu³⁺ ions, stimulated emission cross section and branching ratios. The phonon side band mechanism of ⁵D₂ level of the Eu³⁺ ions in the prepared glass was examined by considering the excitation and Raman spectra. The radiative lifetime calculated using Judd–Ofelt parameters was compared with the experimental lifetime to estimate the quantum efficiency of ⁵D₀ level of Eu³⁺ ions in Li–K–Zn fluorotellurite glass.     

Luminescence properties of CsI:Eu crystals

The work is aimed to research of CsI:Eu single crystals’ luminescence at different excitations in the wide temperature range (from 8 to 300 K) and admixture concentration from 10⁻⁴% up to 10⁻¹% of Eu²⁺ ions. This study was directed to separation of different luminescence mechanisms and luminescence quenching explore. It is found that due to the temperature quenching the room temperature yield is decreased in order of magnitude even for heavy Eu doped CsI crystals. Intense low temperature luminescence band at 441–448 nm connected with Eu²⁺ 4f⁶ 5d → 4f⁷ radiative transition is observed. The results obtained show that the excitonic mechanism plays the main role in energy transfer process to Eu²⁺ ions and this is the reason for relatively low light yield of this emission at RT. The nature of the additional emission bands (410, 450, 480 and 500 nm) are apparently caused by the significant non-isomorphism of cations and/or by the presence of oxygen-containing admixtures.     

Investigation on broadband near-infrared emission in Yb3+/Ho3+ co-doped antimony–silicate glass and optical fiber

In the paper antimony–silicate glass and double-clad optical fiber co-doped with ytterbium and holmium ions were investigated. Absorption spectra in infrared (FT-IR) showed characteristic bands: 445, 605, 1037, 1168 cm⁻¹ coming from the vibration of chemical bonds of SbO₃ and SiO₄, respectively. The combination of relatively low phonon energy with a capability for greater separation (avoiding clustering) of optically active centers in the fabricated glasses should allow an effective expansion of spontaneous emission band. The highest intensity of emission at the wavelength of λ_e = 1950 nm resulting from energy transfer between Yb³⁺ → Ho³⁺ ions was observed in the glass co-doped with 1 mol% Yb₂O₃:0.5 mol% Ho₂O₃. As a result of the optical pumping at the wavelength of 976 nm in the produced optical fiber, strong and narrow band of amplified spontaneous emission (ASE) around 2.1 μm, corresponds to the ⁵I₇ → ⁵I₈ transition, were obtained.     

UV–VUV spectroscopy of rare earth doped persistent luminescence materials

The electronic and defect energy level structure of polycrystalline SrAl₂O₄:Eu²⁺,R³⁺ persistent luminescence materials were studied with thermoluminescence and UV–VUV synchrotron radiation emission and excitation spectroscopy. Theoretical calculations using the density functional theory (DFT) were carried out simultaneously with the experimental work. The experimental band gap energy (E_g) value of 6.6 eV agrees very well with the DFT value of 6.4 eV. The 4f⁷ → 4f⁶5d¹ excitation bands of Eu²⁺ were found rather similar irrespective of the R³⁺ co-dopant. The trap level energy distribution depended strongly on the R³⁺ co-dopant except for the shallowest trap energy above the room temperature remaining the same, however. The different processes in the mechanism of persistent luminescence from SrAl₂O₄:Eu²⁺,R³⁺ was constructed and discussed.     

Optical properties of sol–gel derived Sr2SiO4:Dy3+ – Photo and thermally stimulated luminescence

Trivalent dysprosium-doped strontium silicate (Sr₂SiO₄) phosphors were prepared by sol–gel synthesis using tetra ethyl orthosilicate (TEOS) as precursor. The synthesis temperature could be brought down to 600 °C for formation of a single phase sample. The material was characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), photoluminescence (PL), and thermally stimulated luminescence (TSL). The luminescence study revealed strong ⁴F_9/2 → ⁶H_13/2 transition at 577 nm (yellow), strong ⁴F_9/2 → ⁶H_15/2 transition at 482 nm (blue) and weak ⁴F_9/2 → ⁶H_11/2 transition at 677 nm (red), when excited by 250 nm (Charge transfer band, CTB) or 352 nm (f–f band). The concentration of the dopant ion and the temperature of annealing were optimized for maximum PL intensity. The critical energy-transfer distance for the Dy³⁺ ions was evaluated based on which, the quenching mechanism was verified to be a multipole–multipole interaction. The thermally stimulated luminescence studies of Sr₂SiO₄:Dy³⁺ sample showed main TSL glow peak at 413 K. The trap parameters namely activation energy (E), order of kinetics (b), and frequency factor (s) for this peak were determined using glow curve shape method.     

Novel highly luminescent europium dinitrosalicylates

A series of lanthanide dinitrosalicylates M₃Ln(3,5-NO₂-Sal)₃ · nH₂O (Ln = Eu, Gd; M = Li, Na, K, Cs) was synthesized. It was found that the luminescence efficiency of some M₃Eu(3,5-NO₂-Sal)₃ · nH₂O compounds was near to the high efficiency of europium dibenzoylmethanate with 1,10-phenanthroline, Eu(DBM)₃ · Phen. The luminescence excitation spectra, electron-vibrational luminescence spectra, and vibrational IR spectra were investigated. The energy of the lowest excited triplet state of the ligand was obtained from phosphorescence spectra of M₃Gd(3,5-NO₂-Sal)₃ · nH₂O, M(3,5-NO₂-HSal) · nH₂O, and M₂(3,5-NO₂-Sal) · nH₂O. The details of the structure of compounds were discussed. The influence of different M-cations on the Eu³⁺ luminescence efficiency and on the processes of excitation energy transfer to a Eu³⁺ ion was analyzed. The presence of large alkali metal cations in lanthanide dinitrosalicylates and an increase in the temperature weaken the network of hydrogen bonds and, to some extent, the “ligand–metal” bonds. This is a cause of a long-wavelength shift of the intraligand charge transfer (ILCT) band in Eu³⁺ excitation spectra arising at inclusion of Cs⁺ instead of Li⁺ cations in the crystal lattice and at the heating of compounds. A change of the energies of ligand electronic states at substitution of Li⁺ and Na⁺ for Cs⁺ can give a tenfold enhancement of the Eu³⁺ luminescence efficiency at 300 K.     

Synthesis and luminescence properties of CaAl2O4:Mn4+ phosphor

CaAl_2−yO₄:yMn⁴⁺ (y = 0–1.6 mol%) phosphors are synthesized by a solid-state reaction method in air, and their crystal structure and luminescence property are investigated. To compare luminescence property, CaAl_3.99O₇:1%Mn⁴⁺ and SrAl_1.99O₄:1%Mn⁴⁺ phosphors are also synthesized at the same condition. Broad band excitation spectra are observed within the range 220–550 nm, and emission spectra cover from 600 to 720 nm with the strongest emission peak at ∼658 nm owing to the ²E → ⁴A₂ transition of Mn⁴⁺ ion. The influence of crystal field to luminous intensity is discussed, and the possible luminous mechanism of Mn⁴⁺ ion is explained by using energy level diagram of Mn⁴⁺ ion. CaAl_1.99O₄:1%Mn⁴⁺, CaAl_3.99O₇:1%Mn⁴⁺, and SrAl_1.99O₄:1%Mn⁴⁺ phosphors under excitation 325 nm light emit red light, and their CIE chromaticity coordinates are (0.7181, 0.2813), (0.7182, 0.2818), and (0.7198, 0.2801), respectively. These contents in the paper are helpful to develop novel and high-efficient Mn⁴⁺-doped phosphor for white LEDs.     

Synthesis and spectroscopic characterization of the K4BaSi3O9:Eu3+

K₄BaSi₃O₉:Eu³⁺ polycrystals were synthesized by solid state method. X-ray powder diffraction measurements confirmed structure of the samples. The excitation and the emission spectra of orthorhombic K₄BaSi₃O₉ doped with Eu³⁺ were investigated. The excitation spectrum exhibits a broad band with maximum at 220 nm corresponding to the charge transfer (CT) transition between O²⁻ and Eu³⁺ ions and smaller 4f–4f transitions. The emission of investigated phosphor was excited at 395 nm and has quantum efficiency (QE) equal 27%. The emission maximum at 616.5 nm was assigned to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The luminescence decay profiles as well as the thermal quenching were measured and analyzed. K₄BaSi₃O₉:Eu³⁺has high temperature quenching of the emission T_0.5 = 335 °C.     

Photoluminescence,photo-stimulated luminescence and thermoluminescence properties of CaB2O4 crystals activated with Ce3+

Photoluminescence (PL), photo-stimulated luminescence (PSL), and thermoluminescence (TL) properties of a Ce-doped CaB₂O₄ crystal were studied. The Ce-doped crystal was prepared by the simple solidification method using a Pt crucible under nitrogen atmosphere. A PL emission band in the 350–370 nm wavelength range was obtained under excitation at 325 nm owing to the 5d (t_2g)–4f (²F_5/2, ²F_7/2)-allowed transition of the Ce³⁺ emission center. The fluorescence quantum efficiency and the decay time of Ce³⁺ were estimated to be about 70% and 29 ns, respectively. The 5d–4f emission band of Ce³⁺ also appeared in the 350–370 nm wavelength range in the TL and PSL spectra. Good linear TL and PSL responses were observed in the 1–1000 mGy and 1–10,000 mGy X-ray dose range, respectively.     

EPR,optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr³⁺ were studied by Electron Paramagnetic Resonance (EPR), UV–VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr³⁺-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV–VIS optical absorption spectra of SbPO:Cr³⁺ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from ⁴A₂(F) to ⁴T₁(F), ⁴T₂(F), ²T₁(G), and ²E(G), respectively, of Cr³⁺ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr³⁺ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr³⁺ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr³⁺ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr³⁺-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the ³P₁ → ¹S₀ electronic transition from Sb³⁺ ions. Cr³⁺-doped glasses excited with 415 nm presented Cr³⁺ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (²E → ⁴A₂) and another intense band from 700 to 850 nm (⁴T₂ → ⁴A₂).     

Influence of Yttrium on optical,structural and photoluminescence properties of ZnO nanopowders by sol–gel method

Undoped and Yttrium doped ZnO nanopowders (Zn_1−xY_xO, 0 ⩽ x ⩽ 0.05) were prepared by sol–gel method and annealed at 500 °C for 4 h under air atmosphere. The prepared nanopowders were characterized by powder X-ray diffraction, energy dispersive X-ray spectra, UV–Visible spectrophotometer and Fourier transform infrared spectroscopy. The EDS analysis confirmed the presence of Y in the ZnO system. Both atomic and weight percentages were nearly equal to their nominal stoichiometry within the experimental error. XRD measurement revealed the prepared nanoparticles have different microstructures without changing a hexagonal wurtzite structure. The calculated average crystallite size decreased from 26.1 to 23.2 nm for x = 0–0.02 then reached 24.1 nm for x = 0.05. The change in lattice parameters was demonstrated by the crystal size, bond length, micro-strain and the quantum confinement effect. The observed blue shift of energy gap from 3.36 eV (Y = 0) to 3. 76 eV (Y = 0.05) (ΔE_g = 0.4 eV) revealed the substitution of Y³⁺ ions into ZnO lattice. The presence of functional groups and the chemical bonding are confirmed by FTIR spectra. The appreciable enhancement of PL intensity with slight blue shift in near band edge (NBE) emission from 396 to 387 nm and a red shift of green band (GB) emission from 513 to 527 nm with large reduction in intensity confirm the substitution of Y into the ZnO lattice. Y-doped ZnO is useful to tune the emission wavelength and hence is appreciable for the development of supersensitive UV detector.