On the role of water in some optical properties of alumino-phosphate glasses containing manganese

Optical absorption in broad frequency range (150–5×10⁴ nm) and thermoluminiscence (TL) of the manganese doped alumino-phosphate glasses with two modifiers (Mg, Sr) were measured. It was found that with prolonged melting time the absorption bands at 3·1 m, 5·3 and 5·9 m decrease, new band at 4·2 m appears and that one in UV at about 235 nm increases. Simultaneously the solubility of the glasses in water increases. At longer melted and irradiated glasses the band of electron centres at 210 nm increases while that one of hole centres at 550 nm decreases. These changes are due to the escape of water bonded on two non-bridging oxygens, as well as to the hydrolysis of the melt and oxidation of divalent magnanese. The role of modifiers is also pointed out.The authors would like to express their gratitude to Dr. L.Pajasov á, E.Linhartová and M.Frýbová for careful measurements and PhMr K.ermák for the performing of solubility measurements.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

Optical properties of vanadium-doped bismuth borate glasses before and after gamma-ray irradiation

UV–visible, infrared and Raman spectra, together with thermal properties, were measured for glasses from the system Bi₂O₃–B₂O₃–V₂O₅ before and after successive gamma irradiations. The UV–visible spectrum of the undoped glass before irradiation reveals five UV bands at 210, 275, 310, 350 nm, an intense band at 380 nm and a visible band at 420 nm due to the possible combined presence of trace iron impurities and Bi³⁺ ions. The V-doped glasses reveal six UV bands and two visible bands, probably arising from vanadium ions in three possible valencies, V³⁺, V⁴⁺ and V⁵⁺, beside that due to trace iron impurity beside Bi³⁺ ions. The spectra reveal an obvious resistance of the glasses to successive gamma irradiation. The Raman and infrared spectra show characteristic absorption bands, which indicate the sharing of Bi³⁺ ions as glass-forming (BiO₆) octahedral units together with the presence of various groups of the borate network.     

Absorption,excitation and fluorescence spectra of thallium activated cesium bromide

Absorption, excitation and fluorescence spectra of T1⁺ doped cesium bromide have been investigated at various thallium concentrations. At very low thallium concentration two absorption bands are obtained at 225 nm and 264 nm. With rise of thallium concentration additional absorption bands are obtained at 230, 244, 258, 270 and 285 nm. A single bell-shaped fluorescence band at 357 nm in the ultraviolet region is obtained at low thallium concentration. Two additional visible fluorescence bands appear at 440 and 540 nm with rise in thallium content. The excitation spectra for ultraviolet emission band and visible emission bands are found to be different. Accordingly the ultraviolet emission band is attributed to the characteristic A emission in T1⁺ ion and the visible bands are attributed to dimer centers havingD _4h site symmetry.     

Spectroscopic properties of Mn2+ in new bismuth and lead contained fluorophosphate glasses

Luminescence, absorption and electron spin resonance (ESR) spectroscopic measurements are performed for two new Mn²⁺ doped fluorophosphate glass systems containing bismuth and lead, respectively, i.e., 45Ba(PO₃)₂-55BiF₃ and 45Ba(PO₃)₂-55PbF₂, to elucidate the nature of dopant–ligand bonding in terms of the covalence degree of dopant–ligand bond and ligand field strength. It is found from luminescence measurements that an octahedral coordination of dopant is formed, which is the same as that in fluoroberyllate and phosphate glasses. The optical absorption measurements indicate that the position of the absorption band, ⁴T_1g(G), is red shifted, and the Racah coefficient B is 625 and 627 cm^-1, respectively, as ligand field strength increases in the order of fluoroberyllate, fluorophosphate, phosphate and silicate glasses. The hfs constant A determined from the ESR measurements is 94.33 and 92.12 Oe for two glass systems, respectively. The hfs constant A is also found to be 89.98 Oe and 94.33 Oe in the respective crystalline and glasses 45P₂O₅-55BiF₃. In addition, the resonance observed at g2 in both glass systems is mainly attributed to Mn²⁺ ions in an environment close to octahedral symmetry distorted by agglomeration of resonant centers. It, thus, can be concluded from the ESR measurements that the degree of covalency of dopant–ligand bond in both fluoroberyllate and phosphate glasses is similar, and the crystallization of the glass leads to an increase in the degree of covalency of the ligand–Mn²⁺ bond. PACS 42.70.Ce; 61.43.Fs; 78.55.Qr     

Optical properties of sol-gel fabricated Mn/SiO2 nanocomposites: Observation of surface plasmon resonance in Mn nanoparticles

Manganese nanoparticles were grown in silica glass and silica film on silicon substrate by annealing of the sol-gel prepared porous silicate matrices doped with manganese nitrate. Annealing of doped porous silicate matrices was performed at various conditions that allowed to obtain the nanocomposite glasses with various content of metallic Mn. TEM of Mn/SiO₂ glass indicates the bimodal size distribution of Mn nanoparticles with mean sizes of 10.5 nm and 21 nm. The absorption and photoluminescence spectra of Mn/SiO₂ glasses were measured. In the absorption spectra at 300 nm (4.13 eV) we observed the band attributed to the surface plasmon resonance in Mn nanoparticles. The spectra proved the creation of Mn²⁺ and Mn³⁺ ions in silica glass as well. The absorption spectra of Mn/SiO₂ glasses annealed in air prove the creation of manganese oxide Mn₂O₃. The measured reflection spectra of Mn/SiO₂ film manifest at 240-310 nm the peculiarity attributed to surface plasmons in Mn nanoparticles.     

Low-temperature absorption centers in some simple glasses

At the temperature of liquid nitrogen, glasses were irradiated with Co⁶⁰ radiation and the induced absorption spectra were measured. A strong increase in the 640 nm band was observed in sodium silicate and unleached sodium borosilicate glasses; a new band at 820 nm appeared in potassium silicate glass; and the intensity of the band at 240 nm increased in sodium borate glass and in unleached sodium borosilicate glasses.In conclusion, the authors express their gratitude to N. Z. Andreeva for her assistance in the measurements.     

Optical absorption and emission from irradiated RbMgF3:Eu2+ and KMgF3:Eu2+

The optical properties of irradiated RbMgF₃:Eu²⁺ and KMgF₃:Eu²⁺ have been investigated. Previous research has shown that Eu²⁺ ions in unirradiated RbMgF₃ give rise to broad band absorption around 250 nm and sharp intense line emission at 360 nm. When this material is irradiated little or no change occurs in the 250 nm absorption, but the lifetime of the Eu²⁺ 360 nm transition is reduced. In addition, new emission is observed at 680 nm. In the case of irradiated KMgF₃:Eu²⁺ two new emission bands are observed at 600 and 800 nm. All of these transitions have short lifetimes and are not due to Eu³⁺ ions.     

Emission spectra of KBr:Sn2+

Crystals of KBr:Sn²⁺ irradiated in the A₁, A₂, B or D absorption bands exhibit strong emission in the region of 500 nm. The dependence of this emission on excitation wavelength in the A absorption band shows the 500 nm emission band to be a doublet. This doublet structure is due to electrostatic perturbation from a nearby cation vacancy. It is not possible from emission spectra alone to decide on the actual symmetry of the A_T1 and A_T2 centres responsible for the emission doublet but the various possibilities are discussed. Quenching experiments show that a small emission band at 700 nm is due to Sn²⁺ dimer centres. A series of weak emission bands on the high-energy side of the A_T band are ascribed to emission from the relaxed excited B and D states.     

Luminescence properties and energy transfer in Eu2+, Mn2+ codoped Na(Sr,Ba)PO4 phosphor

Eu²⁺ and Mn²⁺ singly doped and codoped Na(Sr,Ba)PO₄ phosphors were synthesized, and their luminescent properties were investigated. A broad blue emission and a broad orange emission band were observed in Na(Sr,Ba)PO₄:Eu²⁺, Mn²⁺ phosphor. The resonant-type energy transfer from Eu²⁺ to Mn²⁺ was demonstrated, and the energy transfer efficiency was also calculated according to their emission spectra. Based on the principle of energy transfer, the emission intensity ration of Eu²⁺ and Mn²⁺ could be appropriately tuned by adjusting the contents of activators. Due to the strong absorption in the 250–400 nm range, Na(Sr,Ba)PO₄:Eu²⁺, Mn²⁺ phosphor could be used as a potential candidate for near-UV white light-emitting diodes (LEDs).     

Luminescent properties of Sr5(PO4)3 Cl:Eu2+, Mn2+ as?a?potential phosphor for UV-LED-based white LEDs

Eu²⁺ and Mn²⁺ co-activated Sr₅(PO₄)₃Cl phosphors with blue and orange color double emission bands, under a broad-band excitation wavelength range of 340–400 nm, were synthesized by the solid-state reaction. It was found that the processing parameters, including the fluxes, annealing time and activators concentrations, affect the emission intensity and other luminescent properties. Energy transfer between Eu²⁺ and Mn²⁺ was discovered and the transfer efficiency was also estimated based on relative intensities of Eu²⁺ and Mn²⁺ emission. Thus the relative strength of blue and orange emission intensities could be tuned by varying the relative concentration of Eu²⁺ and Mn²⁺. Since the photoluminescence excitation spectra of the newly developed Sr₅(PO₄)₃Cl:Eu²⁺, Mn²⁺ phosphors exhibit a strong absorption in the range of 340–400 nm, they are promising for producing UV-LED-based white LEDs.     

Interactions of gamma rays with undoped and Mn-doped sodium phosphate glasses

Ultraviolet and visible spectroscopic measurements were used to investigate prepared undoped and Mn-doped sodium phosphate glasses before and after successive gamma irradiation. The effects of both glass composition and MnO₂ content on the generation of radiation-induced defects were investigated. Undoped sodium phosphate glass shows strong UV absorption, which is attributed to the presence of trace iron impurities present in the raw materials. Mn-doped glasses reveal an additional visible broad band centered at about 500 nm due to Mn³⁺, which has recently been related to the ⁵E_g →⁵T_2g transition. The radiation-induced bands are correlated with the generation of liberated electron–hole pairs during the process of gamma irradiation and the possibility of photochemical reactions especially with trace iron impurities and manganese ions. The intensity and the position of the induced bands are observed to depend on the type and composition of glass, concentration of the dopant and also on the irradiation dose. Manganese ions when present in relatively higher content have been found to show a shielding behavior towards the effects of progressive gamma irradiation causing a retardation of the growth of the induced defects. Infrared and Raman spectra of the undoped and Mn-doped glasses were measured to investigate the structural phosphate groups present and the effect of MnO₂ on the network structure. An ESR investigation was carried out to confirm the state of manganese ions in the prepared sodium phosphate glasses.     

Radiolysis of LaF<Subscript>3</Subscript> crystals with rare-earth impurities

The absorption spectra of LaF₃ crystals, both pure and doped with rare-earth fluorides (YF₃, CeF₃, NdF₃, PrF₃, SmF₃, EuF₃, GdF₃, TbF₃, DyF₃, HoF₃, ErF₃, TmF₃, YbF₃, and LuF₃) have been investigated. All these impurities can be separated into two groups with respect to the shape of the absorption spectra of irradiated crystals. The spectra of the crystals doped with Nd, Sm, Tm, and Yb exhibit, along with 200-nm hole band F₃^-, weak bands due to RE²⁺-anion vacancy centers. The spectra of LaF₃ crystals with Y, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu impurities exhibit, along with the hole-center bands (F₃^- at 200 nm and V_kA at 320 nm), bands of comparable intensity, which can be attributed to RE³⁺–F centers. This conclusion is confirmed by preliminary quantum-chemical calculations and the estimation of the levels location in the energy-band diagram.     

Preparation and characterization of Zn2SiO4: Mn phosphors with hydrothermal methods

Mn²⁺-doped Zn₂SiO₄ phosphors had been prepared by hydrothermal method in stainless-steel autoclaves. Effects of synthesized methods, reaction temperature, ambience of heat treatment on the structure and the luminescence properties of this silicate were studied with X-ray diffraction apparatus (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and fluorescence spectrum. Results show that Zn₂SiO₄ nanocrystalline can be obtained by hydrothermal method at relatively low temperatures. The absorption pattern shows an absorption edge at about 380 nm originated from ZnO crystals and two absorption bands at about 215 and 260 nm. Mn²⁺-doped Zn₂SiO₄ has a luminescence band with the wavelength at about 522 nm under 255 nm excitation, and the luminescent intensity increases after being heat treated.     

Y-Absorptionsbande im bestrahlten LiF

The absorption measurements at a constant and uniformly increasing temperature and the thermostimulated electron emission and luminescence of with α-, cathode- andγ-rays irradiated LiF crystals were performed and the conditions of the formation of a new absorption band at about 500 nm investigated. It turned out that the band in α-irradiated samples is composed from two and inγ-irradiated from three bands. In this case the short-wave-length-band with the zero-phonon-line at 491 nm is very probably the well knownF ₃ ^t -band. The long-wave-length-band with the zero-phononline at 507 nm (theX band) is of unknown nature. TheY band lies at 494,3 nm (at 77 ?K) and its nature could consist in the colour centre agglomerates.     

Vibronic excitation spectrum of alkali aluminometaphosphate glasses containing uranium

The absorption, excitation and emission spectra of metaphosphate glasses MPO₃.Al(PO₃)₃ (M = Li, Na, K) doped with 1 or 2 w.% of uranium oxide have been measured at room temperature. The spectra were compared with those of solid uranyl nitrate and its water solution. The excitation band of glasses peaking at about 420 nm shows a great deal of structure like that of the solution. The diffuse structure would be due to the electron vibronic transitions in the uranium centre of a molecular form (probably uranyl (UO₂)²⁺).     

Optical properties of Cu+ centers in NaCl

Different aggregation-precipitation states of Cu⁺ have been characterized by absorption bands peaked at 305, 350 and 372–383 nm.The absorption bands at 372–383 nm, observed exclusively in the most doped crystal, have been associated with the Z₁₂, Z₃ excitons of CuCl microcrystals incorporated into the NaCl matrix Their positions shift to low energies with increasing concentration, as expected for a decrease in the stress over the precipitate.The Z1₁₂, Z₃ exciton bands of CuCl microcrystals precipitated in NaCl can be observed by the optical absorption spectrum without reaching saturation Therefore, this technique could be an alternative method to studies of CuCl thin-film depositions or reflectivity of CuCl single crystals.The red emission band observed at 600 nm is a long-lived emission (τ? 29 ms) at variance with the behavior reported for the Cu⁺ emission It is related to energy transfer processes from Cu⁺ to Mn²⁺.     

Synthesis,vibrational and UV–visible studies of sodium cadmium orthophosphate

In this paper, NaCdPO₄ orthophosphate was prepared by solid-state reaction technique at high temperature. Structural, vibrational and optical properties have been investigated. X-ray powder diffraction analysis revealed that the titled compound crystallizes in the orthorhombic system with Pmnb space group. Vibrational study by means of Raman and FTIR spectroscopies confirms the existence of the (PO₄)^3? functional group. Optical properties were recorded at room temperature using UV–visible spectroscopy in the spectral range (200–800) nm. The UV–Vis absorption bands are attributed to the charge transfer from the oxygen ligands to the central phosphate atom inside the PO₄ ^3? groups. The optical absorbance was measured also to determinate the optical band gap using Kubelka–Munk function. The dispersion parameters (E₀ and E_d) of this compound were estimated using the Wemple Di-Domenico model.     

Absorption of CaF2 crystals containing lead and oxygen

The absorption in the vacuum and near ultraviolet region of CaF₂ crystals containing lead and oxygen has been measured. Two main absorption bands at 155 and 202 nm are presumably due to lead centres and the band at 206 nm to oxygen. The nature of the weak band at 166 nm remains obscure. The absorption below 145 nm is probably due to excitons.The authors would like to express their gratitude to Ing. E.Mariani, CSc., for his interest and helpful discussions during the course of this work.     

Optical properties of pyridine funtionalized TbF<Subscript>3</Subscript> nanoparticles

The preparation of pyridine functionalized TbF₃ nanoparticles are described in this report. Synthesized nanoparticles were characterized using the TEM, UV/Vis, FTIR and photoluminescence spectroscopy. TEM micrograph reveals the nanorod shaped, uniform in size with a particles size in the range of 20–30 nm. FTIR spectrum shown characteristic absorption bands of pyridine and a small intensity band at 411 cm⁻¹ corresponding metal nitrogen ν(Tb–N) bonding. Uv-vis spectrum shown the characteristic absorption transitions of Tb³⁺ ion. A strong emission transition at 540 nm (⁵D₄ → ⁷F₅) was observed on excite by visible light at 414 nm.