Energy transfer in LaMgB5O10:Pr,Mn under VUV excitation

Luminescent properties of Pr³⁺ or Mn²⁺ singly doped and Pr³⁺, Mn²⁺ co-doped LaMgB₅O₁₀ are investigated by synchrotron radiation VUV light. When LaMgB₅O₁₀:Pr³⁺ is excited at185 nm, the photon cascade emission between 4f levels of Pr³⁺ is observed. In the excitation spectra of LaMgB₅O₁₀:Mn²⁺ monitoring the 615 nm emission of Mn²⁺, several excitation bands in a spectral range from 330 to 580 nm are recorded, among which the most intense band is centered at 412 nm (⁶A_1g→⁴E_g-⁴A_1g). This band has considerable spectra overlap with the 410 nm emission (¹S₀→¹I₆) of Pr³⁺, which is favorable for energy transfer from Pr³⁺ to Mn²⁺. Such energy transfer is observed in the co-doped sample, converting the violet emission (410 nm) of Pr³⁺ into the red emission (615 nm) of Mn²⁺. The concentration dependence of transfer efficiency is also investigated.     

A novel blue-emitting phosphor: BaAl2B2O7: Pb

Pb²⁺ doped BaAl₂B₂O₇ materials were prepared by a solution combustion synthesis. The phase of the synthesized materials was determined using the powder X-ray diffraction. The photoluminescent properties of Pb²⁺ doped BaAl₂B₂O₇ materials were investigated using spectrofluorometer at room temperature. The emission and excitation bands of BaAl₂B₂O₇: Pb²⁺ were observed at 423 and 266 nm, respectively. The dependence of the emission intensity on the Pb²⁺ concentration for BaAl₂B₂O₇: Pb²⁺ was investigated. The Stokes shifts of BaAl₂B₂O₇: Pb²⁺ was calculated to be 13 953 cm⁻¹.     

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.     

Emission spectra of MgSO4:Dy,MgSO4:Tm and MgSO4:Dy,Mn phosphors

MgSO₄:Dy, MgSO₄:Tm and MgSO₄:Dy,Mn thermoluminescence (TL) phosphors have been prepared and their emission spectra were measured using a linear heater and optical multichannel analyzer. Emission bands at about 480, 580 and 660 nm of MgSO₄ doped with Dy were observed in three dimension (3D) glow curve. Emission bands about 360, 460, and 660 nm were observed in a 3D glow curve of MgSO₄ doped with Tm. The emission spectra of MgSO₄:Dy and MgSO₄:Tm are attributed to the characteristic emission wavelengths from transitions of Dy³⁺ and Tm³⁺ respectively. The results show that the structures of traps in matrix materials determine the activation energy distribution and dopant energy levels of rare earth ions are related with the emission spectrum wavelengths of sulfate phosphors. The intensities of the glow peaks in both bands at about 480 and 580 nm in MgSO₄ doped Dy and Mn were dramatically reduced in comparison with that of MgSO₄ doped Dy except above 300°C. It means that the trapping structures of MgSO₄ :Dy phosphor has greatly been altered by the co-dopant Mn but no change is observed in wavelengths of the emission spectra.     

Yellow-orange light emission from Mn2+-doped ZnS nanoparticles

ZnS nanoparticles with Mn²⁺ doping (1–2.5%) have been prepared through a simple soft chemical route, namely the chemical precipitation method. The nanostructures of the prepared undoped ZnS and Mn²⁺-doped ZnS:Mn nanoparticles have been analyzed using X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–vis spectrophotometer. The size of the particles is found to be in 2–3 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample only exhibits a blue-light emission peaked at ∼365 nm under UV excitation. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn^{2+ 4}T₁–⁶A₁ transition is observed along with the blue emission. The prepared 2.5% Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission at ∼580 nm with the blue emission suppressed.     

Synthesis and photoluminescence of LiCaBO3: M (M: Pb2+ and Bi3+) phosphor

Pure, Pb²⁺ and Bi³⁺ doped LiCaBO₃ materials were prepared by a solution combustion synthesis method. The phase of LiCaBO₃ were determined using the powder XRD and FTIR. The photoluminescent properties of Pb²⁺ and Bi³⁺ doped LiCaBO₃ materials were investigated using spectrofluorometer at room temperature. The emission bands of LiCaBO₃: Pb²⁺ and LiCaBO₃: Bi³⁺ were observed at 296 and 378 nm, respectively. LiCaBO₃ with different Pb²⁺ and Bi³⁺ doping concentrations were analyzed at room temperature. The Stokes shifts of LiCaBO₃: Pb²⁺ and LiCaBO₃: Bi³⁺ were calculated to be 3952 and 6440 cm^?1, respectively.     

Magnetic and luminescent properties of manganese-doped ZnSe crystals

Magnetic and photoluminescent properties of manganese-doped ZnSe crystals with different impurity concentrations were investigated. The concentration of Mn²⁺ ions in ZnSe crystals has been varied from 0.01 to 0.3 at%. Magnetic and photoluminescent studies have confirmed the introduction of Mn in ZnSe crystals. It was established that Mn²⁺ ions are responsible for the emission bands with maximum at 616 nm and 633 nm, which correspond to ⁴T₂→⁶A₁ and ⁴T₁→⁶A₁ intracentre transitions of Mn²⁺ ions respectively. It was found that the concentration quenching of the photoluminescent bands is associated with Mn²⁺ ions, which are due to the formation of Mn–Mn clusters. Magnetic properties studies have shown that at high doping levels the manganese atoms form Mn–Mn clusters in ZnSe. From the temperature dependence of magnetic susceptibility of ZnSe:Mn crystals that follows the Curie–Weiss law, it was possible to estimate the Curie–Weiss temperature Θ(x) and the effective Mn–Mn antiferromagnetic exchange constant (J₁).     

Synthesis, characterization and optical properties of water-soluble ZnS:Mn nanoparticles

ZnS nanoparticles with Mn²⁺ doping (0.5-20%) have been prepared through a simple chemical method, namely the chemical precipitation method. The structure of the nanoparticles has been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV-vis spectrometer. The size of the particles is found to be 3-5 nm range. Photoluminescence spectra were recorded for undoped ZnS nanoparticles using an excitation wavelength of 320 nm, exhibiting an emission peak centered at around 445 nm. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn²⁺⁴T₁-⁶A₁ transition is observed along with the blue emission. The prepared Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission 580 nm with the blue emission suppressed. The maximum PL intensity is observed only at the excitation energy of 3.88 eV (320 nm). Increase in stabilizing time up to 48 h in de-ionized water yields the enhancement of emission intensity of doped (4% Mn²⁺) ZnS. The correlation made through the concentration of Mn²⁺ versus PL intensity resulted in opposite trend (mirror image) of blue and yellow emissions.     

Oxygen vacancy and dopant concentration dependent magnetic properties of Mn doped TiO2 nanoparticle

Mn doped TiO₂ nanoparticles are synthesized by sol–gel method. Incorporation of Mn shifts the diffraction peak of TiO₂ to lower angle. The position and width of the Raman peak and photoluminescence intensity of the doped nanoparticles varies with oxygen vacancy and Mn doping level. The electron spin resonance spectra of the Mn doped TiO₂ show peaks at g = 1.99 and 4.39, characteristic of Mn²⁺ state. Reduction in the emission intensity, on Mn doping, is owing to the increase of nonradiative oxygen vacancy centers. Mn doped TiO₂, with 2% Mn, shows ferromagnetic ordering at low applied field. Paramagnetic contribution increases as Mn loading increases to 4% and 6%. Temperature dependent magnetic measurement shows a small kink in the ZFC curve at about 40 K, characteristic of Mn₃O₄. The ferromagnetic ordering is possibly due to the interaction of the neighboring Mn²⁺ ions via oxygen vacancy (F⁺ center). Increase in Mn concentration increases the fraction of Mn₃O₄ phase and thereby increases the paramagnetic ordering.     

Absorption phenomena in multicomponent phosphate glasses with Mn

The absorption and ESR spectra of multicomponent alumino-phosphate glasses doped with manganese (0·2–20 mol %) has been measured and compared with the absorption spectra of manganous and manganic ions in model solutions. The unirradiated glasses show in ultraviolet region increasing absorption below 200 nm with the shoulder at 235 nm and the absorption bands due to manganous oxygen complexes in octahedral symmetry. They are similar to the absorption bands of Mn²⁺ in concentrated H₃PO₄ acid. In irradiated glasses the bands at 200, 235, 275 (only if Mn is present) and a broad band at 540 nm appear. After the annealing at 450 C all radiation-induced bands disappear and the bands at 235 nm is more pronounced. The Mn³⁺ in H₃PO₄ solution exhibit the absorption spectrum with a weak band at 530 nm and a very intense band at 270 nm. It is therefore proposed that both the 540 and 275 nm bands in irradiated glasses can be assigned to octahedral oxygen complexes of Mn³⁺, i.e. to hole centres. The band at 200 nm which is practically independent of the modifiers (Be, Mg, Ca, Sr and Ba) is, therefore, associated with electron centres (electrons trapped in non-bridging oxygen vacancies). It is suggested that the band at 235 nm in irradiated and annealed glasses is associated with irreversible structural changes.The authors wish to express their appreciation to H.Dvoáková for preparing the solutions and E.Linhartová for careful measurements.     

Photoluminescence properties of Eu and Mn-activated BaMgP2O7 as a potential red phosphor for white-emission

A phosphate compound, BaMgP₂O₇ was co-doped with Eu²⁺ and Mn²⁺ for making a red-emitting phosphor. The phosphor was prepared by a solid-state reaction at high temperature. The photoluminescence properties were investigated under ultraviolet (UV) ray excitation. From a powder X-ray diffraction (XRD) analysis, the formation of single-phased BaMgP₂O₇ with a monoclinic structure was confirmed. In the photoluminescence spectra, the BaMgP₂O₇:Eu,Mn phosphor emits two distinctive colors: a blue band centered at 409 nm originating from Eu²⁺ and a red band at 615 nm caused by Mn²⁺. Also, efficient energy transfer from Eu²⁺ to Mn²⁺ in the BaMgP₂O₇:Eu,Mn system was verified by observing that the excitation spectra of BaMgP₂O₇:Eu,Mn emitted at 409 and 615 nm by Eu²⁺ emission and Mn²⁺ emission, respectively, are almost the same as that of BaMgP₂O₇:Eu monitored at 409 nm. The optimum concentration of Eu²⁺ ions in BaMgP₂O₇:0.015Eu excited at 309 nm wavelength is 1.5 mol%. With an increase of Mn²⁺ content up to 17.5 mol%, a systematic decline in the intensity of the excitation spectrum by Eu²⁺ and a gradual growth in the intensity of emission band by Mn²⁺ were observed. Accordingly, the optimum concentration of Mn²⁺ in BaMgP₂O₇:0.015Eu,Mn is 17.5 mol%. The maximum spectral overlap between emission of Eu²⁺ and excitation of Mn²⁺ is achieved in a composition of BaMgP₂O₇:0.015Eu,0.175Mn, resulting in considerable red-emission at 615 nm.     

Manifestation of up-conversion in Yb3+/Tm3+ doped Li2O–Y2O3–SiO2 glass system

In this study, we have investigated the principal role of Y₂O₃ on the emission features of Tm³⁺ ion and up-conversion phenomenon in Tm³⁺ and Yb³⁺ co-doped Li₂O–Y₂O₃–SiO₂ glass system. The concentration of Y₂O₃ is varied from 0 to 5 mol% while that of Yb³⁺ and Tm³⁺ is fixed. When the glasses are doped with Tm³⁺ ions, the intense blue and red emissions were observed, whereas Yb³⁺ doped glasses exhibited NIR emission at about 980 nm. When the glasses are co-doped with Tm³⁺ and Yb³⁺ ions and excited at 900 nm, the blue and red emission lines were observed to be reinforced and strengthened with increase in the concentration of Y₂O₃. The IR emission band detected at about 1.8 μm due to ³F₄ → ³H₆ transition of Tm³⁺ ions is also observed to be strengthened due to co-doping. The reasons for enhancement in the intensity of various emission bands due to co-doping have been identified and discussed with the help of rate equations for various emission transitions.     

Luminescence spectroscopy and energy transfer in Eu2+/Mn2+-doped KCaPO4 phosphors

Eu²⁺/Mn²⁺-doped KCaPO₄ phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), SEM, photoluminescence excitation, and emission spectra, and the luminescence decay curves were measured. Mn²⁺ singly doped KCaPO₄ shows the weak origin-red luminescence band peaked at about 590 nm. The Eu²⁺/Mn²⁺ co-doped phosphors emit two distinctive luminescence bands: a blue one centered at 480 nm originating from Eu²⁺ ions and a broad red-emitting one peaked at 590 nm from Mn²⁺ ions. The luminescence intensity from Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ ions. The efficient energy transfer from Eu²⁺ to Mn²⁺ was verified by the photoluminescence spectra together with the luminescence decay curves. The resonance-type energy transfer via a dipole–quadrupole interaction mechanism was supported by the decay lifetimes. The emission colors could be tuned by changing the Mn²⁺-doping concentration.     

Luminescent characteristics of ZrO<Subscript>2</Subscript>:Pb nanopowders

ZrO₂ nanopowders doped with Pb ions are prepared by the coprecipitation method. The average size of the powders, measured by X-ray diffraction, is 4–6 nm. The emission spectra show a narrow band originating from the transition from the ¹S₀ ground state to the ³P₁ excited state of the Pb ions. A quenching of the photoluminescence is observed when the concentration of Pb²⁺ is higher than 5%. The influence of residual chlorine ions on the luminescent properties of the nanopowders is also discussed. PACS 78.55.-m; 81.05.Je; 61.72.Ww     

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.     

Luminescence characterization and electron beam induced chemical changes on the surface of ZnAl2O4:Mn nanocrystalline phosphor

Luminescence characteristics and surface chemical changes of nanocrystalline Mn²⁺ doped ZnAl₂O₄ powder phosphors are presented. Stable green cathodoluminescence (CL) or photoluminescence (PL) with a maximum at ∼512 nm was observed when the powders were irradiated with a beam of high energy electrons or a monochromatic xenon lamp at room temperature. This green emission can be attributed to the ⁴T₁ → ⁶A₁ transitions of the Mn²⁺ ion. Deconvoluted CL spectra resulted in two additional emission peaks at 539 and 573 nm that may be attributed to vibronic sideband and Mn⁴⁺ emission, respectively. The luminescence decay of the Mn²⁺ 512 nm emission under 457 nm excitation is single exponential with a lifetime of 5.20 ± 0.11 ms. Chemical changes on the surface of the ZnAl₂O₄:Mn²⁺ phosphor during prolonged electron beam exposure were monitored using Auger electron spectroscopy. The X-ray photoelectron spectroscopy (XPS) was used to determine the chemical composition of the possible compounds formed on the surface as a result of the prolonged electron beam exposure. The XPS data suggest that the thermodynamically stable Al₂O₃ layer was formed on the surface and is possibly contributing to the CL stability of ZnAl₂O₄:Mn phosphor.     

Quantitative electron microprobe analysis of commercial microcrystalline phosphor powders

Quantitative chemical analysis of individual particles from three commercial willemite fluorescent lamp powders (Zn₂SiO₄:Mn) has been made using an electron microprobe. A simple interference type spectrometer attachment and photomultiplier readout also allowed simultaneous recording of cathodoluminescence spectra of individual particles. There is significant grain-to-grain variation in the Zn/Mn and Zn/Si ratios calibrated against single-crystal material. In addition to the usual green particles, occasional orange and blue luminescing particles are observed in all the samples studied. Spectra of orange particles, which had higher concentrations of Mn, show two broad bands with peaks around 5300 Å and 5900 Å. Comparison with single crystals, artificially doped with Mn, suggest that the orange particles have a second phase, with tephroite structure, present along with willemite phase. Mn²⁺ in tephroite is six-fold coordinated, thus luminescence emission from this phase would be in the red region in comparison to Mn²⁺ in the willemite structure where it is four-fold coordinated.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Effect of Pb2+ ions on the photoluminescence characteristics of Mn2+-doped Zn2SiO4

Zn₂SiO₄ single-doped and co-doped with Mn²⁺ ions and Pb²⁺ ions has been prepared by a sol–gel process. The luminescent properties of the samples have been investigated. From the excitation and emission spectral analysis, it was found that the emission peaks vary with the change of the excitation wavelength. An enhanced luminescent characteristic of Mn²⁺ ions (in blue and green spectral zones) has been observed, due to the energy transfer from the Pb²⁺ ion to the Mn²⁺ ion. The emission peaks originate from the d–d transitions of the Mn²⁺ ion. However, the relative intensities of the peaks show a dependence on the concentration of the Pb²⁺ ion. PACS 81.05.Je; 78.55.Hx; 61.72.Ww     

Color improvement of white-light through Mn-enhancing yellow-green emission of SrSi2O2N2:Eu phosphor for white light emitting diodes

Photoluminescence (PL) enhancement of SrSi₂O₂N₂:Eu and the resultant color improvement of white-light were investigated via co-doping Mn with Eu. We observed that a unique absorption of host lattice of SrSi₂O₂N₂ and its visible band emission peaked at around ∼550 nm for SrSi₂O₂N₂:Mn²⁺ in the wavelength range of 450-600 nm. This highly eye-sensitive ∼550 nm-peaked band emission of SrSi₂O₂N₂ doped with Mn²⁺ happens to overlap the 535 nm-peaked band emission of SrSi₂O₂N₂ doped with Eu²⁺, resulting in an intensified photoluminescence in a maximum by 355%. By combining this as-prepared Mn intensified SrSi₂O₂N₂:Eu phosphor with blue InGaN chip, the quality of white-light was improved to 93.3% for color rendering index and 3584 K for correlated color temperature.