Influence of high hydrostatic pressure on Eu-luminescence in KMgF3:Eu crystal

Spectroscopic investigations are presented of KMgF₃:Eu²⁺ crystal under high hydrostatic pressure from ambient to 310 kbar. The sample was excited by 30 ps pulses generated by optical parametric generator (OPG) system with wavelength controlled between 210 and 325 nm. The Grüneisen parameters of individual phonons are obtained from the pressure shift of the Eu²⁺ emission related to the ⁶P_7/2→⁸S_7/2 transition accompanied by phonon sideband. The luminescence decays exponentially for the pressure below 135 kbar with lifetime of 3.30 ms and slightly nonexponential above 135 kbar, while the average decay time is nearly independent of the pressure. The results obtained for KMgF₃:Eu²⁺ are compared with those for LiBaF₃:Eu²⁺ in which the ⁶P_7/2→⁸S_7/2 emission is replaced by the broadband emission of the 4f⁶5d¹→4f⁷ transition at high hydrostatic pressure.     

Luminescence of Ca(NbO3)2:Pr at ambient and high hydrostatic pressure

In this contribution, photoluminescence and time-resolved photoluminescence spectra of Ca(NbO₃)₂ doped with Pr³⁺ obtained at high hydrostatic pressure up to 72 kbar applied in a diamond anvil cell are presented. At ambient conditions, the emission spectrum obtained in the time interval 0-1 μs is dominated by spin-allowed transitions from the ³P₀ state. On the other hand, transitions from ¹D₂, characterized by a decay time equal to 30 μs dominate the steady-state luminescence.At pressures lower than 60 kbar, the continuous wave emission spectrum consists of sharp lines peaking between 600 and 625 nm, related to the ¹D₂→³H₄ transition and three lines at 500, 550 and 650 nm related to emission transitions originating from the ³P₀ level of Pr³⁺. The emission from the ¹D₂ excited state depends weakly on the pressure. Its decay time decreases from 33 μs at ambient pressure to less than 22 μs at 68 kbar. On the other hand, the ³P₀ emission is strongly pressure dependent. At pressures of 60 kbar and higher, the Pr³⁺ emission intensity from the ³P₀ state decreases. This is accompanied by a strong shortening of the luminescence decay time.The observed pressure quenching of the f-f emission transitions and the concomitant lifetime shortening have been attributed to increasing crossover from the ³P₀ state of Pr³⁺ to a Pr³⁺-trapped exciton state.     

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.     

High-pressure optical studies of Y2O3:Eu3+ nanoparticles

Abstract

The fluorescence spectra of Y₂O₃:Eu³⁺ nanoparticles have been measured under the pressure of up to 78 kbar at room temperature. In this pressure range, a red-shift of 0.02(1) nm/kbar^?1 is noticed for the 0–2 line (⁵D₀→⁷F₂ transition). This shift is explained by the change of negative charge of the surrounding ligands. Compatibility between measured and calculated values for the 0–2 line position was obtained. The luminescence decay curves of the ⁵D₀→⁷F₂ transition were studied up to 78 kbar and were found to behave exponentially for all pressures studied. The fluorescence lifetime τ for the 0–2 line (⁵D₀→⁷F₂ transition) slowly decreased with pressure. The pressure effect on τ for the 0–2 line (⁵D₀→⁷F₂ transition) was explained by a model which considers the pressure effect on the line position, inter-ionic distance, ion volume and polarizability, molecular volume and polarizability, molecular refractive index and the refractive index medium n _med of the surrounding hydrostatic medium. The fluorescence lifetime calculated by the present model is in close correspondence with the experimental values.     

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.     

Pressure dependence of spectral positions and widths of emission lines related to DJ→FJ electronic transitions in Sm ions doped into SrFCl single crystal

The pressure dependence of the peak positions and widths of the fluorescence lines corresponding to the ⁵D_J→⁷F_J electronic transitions in Sm²⁺-doped SrFCl crystals was measured at room temperature (RT) with a diamond anvil cell (DAC) and a high-pressure gas system, using silicone oil and gaseous helium as the pressure-transmitting medium, respectively. At RT and ambient pressure the electronic transitions ⁵D₀→⁷F_J (J= 0, 1, 2, 3) and ⁵D₁→⁷F_J (J=0, 1, 2) in Sm²⁺ ions yielded rather sharp spectral lines peaked at 14490, 14206, 13685, 13012 cm⁻¹ and 15823, 15533, 15012 cm⁻¹, respectively. At pressures up to 45 kbar in the DAC all these peaks shifted linearly to lower energies at the rates −2.36, −2.10, −2.43, −2.22 cm⁻¹/kbar and −2.35, −2.33, −2.47 cm⁻¹/kbar. Under purely hydrostatic gas pressure up to 7 kbar at RT the initial (normal pressure) widths of the ⁵D₀→⁷F₀, ⁵D₀→⁷F₁ and ⁵D₁→⁷F₀ lines having a Lorentzian profile (with corrected FWHM values of 1.55, 5.71 and 1.97 cm⁻¹) decreased linearly with increasing pressure at the rates −0.009(2), −0.077(3) and −0.034(2) cm⁻¹/kbar, respectively. Possible mechanisms of the observed pressure effects are discussed. For further studies of linewidth variations with the pressure, gaseous helium as a best possible high-pressure medium is strongly recommended.     

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.     

Low temperature magnetoresistance in La1.32Sr1.68Mn2O7 layered manganite under hydrostatic pressure

The La_1.32Sr_1.68Mn₂O₇ layered manganite system has been studied by the low temperature electrical resistance and magnetoresistance under hydrostatic pressure up to 25 kbar. We have observe both, a Curie temperature (T_C) and a metal-insulator transition (T_MI) at 118 K in the ambient pressure. The applied pressure shifts the T_MI to higher temperature values and induces a second metal-insulator transition (T²_MI) at 90 K, in the temperature dependence of resistivity measurements. Also, the pressure suppresses the peak resistance abruptly at T_C. When an external field of 5 T is applied, we have observed a large negative magnetoresistance of 300% at the transition temperature and a 128% at 4.5 K. However, the increased pressure decreases the magnetoresistance ratio gradually. When the pressure reaches its maximum available value of 25 kbar, the magnetoresistance ratio decreases at a rate of 1.3%/kbar. From our experimental results, the decrease of magnetoresistance ratio with pressure is explained by the pressure induced canted spin state which is not favor for the spin polarized intergrain tunneling in layered manganites.     

Photoluminescence properties of Sm-doped BaBr2 under hydrostatic pressure

Photoluminescence spectra of Sm²⁺-doped BaBr₂ have been measured under hydrostatic pressures up to 17 GPa at room temperature. In the low pressure range a red-shift of the broad 5d-4f transition of −145 cm⁻¹/GPa is observed. From 5 to 8 GPa a phase mixture of the initial orthorhombic phase and the high-pressure monoclinic phase gives rise to two 5d-4f bands, which are strongly overlapping. Above 8 GPa the crystal is completely transformed to its high-pressure phase where two different Sm²⁺ sites exist, but only one broad 5d-4f transition is detected. It exhibits a red-shift of −36 cm⁻¹/GPa. In addition, the line shifts of the ⁵D₀→⁷F_J (J=0, 1, 2) transitions are investigated. Linear shifts of −19 cm⁻¹/GPa for J=0, 2 and of −13 cm⁻¹/GPa for J=1 are observed in the pressure range from 0 to 5 GPa.     

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.     

Role of Al coordination in barium phosphate glasses on the emission features of Ho ion in the visible and IR spectral ranges

The glasses of the composition (39−x)BaO-xAl₂O₃-60P₂O₅:1.0Ho₂O₃ (in mol%) with x value ranging from 1.0 to 4.0 have been synthesized. The IR spectral studies of these glasses have indicated that there is a gradual transformation of Al³⁺ ions from tetrahedral to octahedral with increase in the concentration of Al₂O₃ up to 3.0 mol%. Optical absorption and fluorescence spectra (in the visible and NIR regions) of these glasses have been recorded at room temperature. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of Ho³⁺ ions in these glasses. From the luminescence spectra, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and emission cross-section σ^E for various emission levels of these glasses have been evaluated. The radiative lifetime of the ⁵S₂→⁵I₈ (green emission) transition has also been measured. The variations observed in these parameters have been discussed in the light of varying co-ordinations (tetrahedral and octahedral positions) of Al³⁺ ions in the glass network. The influence of hydroxyl groups on the luminescence efficiency of the transition ⁵S₂→⁵I₈ has also been discussed. Finally the optimum concentration of Al₂O₃ for getting maximum luminescence output has also been identified and reported.     

Optical and photophysical investigation of Meso, Proto and Hematoporphyrin(IX)dimethylester doped hybrid borate glasses

Hybrid borate glasses containing different concentrations (0.5-2.0 mg in 12 g of boric acid) of Mesoporphyrin(IX)dimethylester, Protoporphyrin(IX)dimethylester and Hematoporphyrin(IX)dimethylester were prepared by rapid melt quench technique at 230 °C. The hybrid glass samples were characterized by X-ray diffraction, optical absorption, steady state and time-resolved fluorescence emission. The optical absorption spectrum shows red-shift in Soret band along with change in Q-band pattern. The intensity of Q-band was found to increase with increase in the concentration of porphyrin in the glass. Steady state emission spectrum shows strong S₂→S₀ emission in the range 462-495 nm and blue shift in S₁→S₀ emission. Time-resolved fluorescence emission and fluorescence excitation spectra showed that different structures of porphyrins were exist in the glass samples. The variation in the spectral behaviour in the glass was correlated with those in solution medium and possible structures of porphyrin in borate glass were explored.     

Influence of ligand coordination of cobalt ions on structural properties of ZnO-ZnF2-B2O3 glass system by means of spectroscopic studies

The glasses of the composition 10ZnO-30ZnF₂-60B₂O₃ doped with different concentrations of CoO were prepared. Differential scanning calorimetric (DSC) studies, optical absorption, photoluminescence and infrared spectra of these glasses have been carried out. DSC studies have indicated that the resistance of the glass against devitrification increases with the increase in the concentration of CoO. Optical absorption spectra have exhibited one octahedral band due to ⁴T_1g(F)→²T_1g(H) and two tetrahedral bands due to ⁴A₂(⁴F)→⁴T₁(⁴P) ⁴A₂(⁴F)→⁴T₁(⁴F) transitions of Co²⁺ ions at about 525, 570 and 1400 nm, respectively. As the concentration of CoO is increased the tetrahedral bands are observed to grow at the expense of octahedral band. The luminescence spectra have exhibited two emission bands in the spectral regions of 600-700 nm and 800-900 nm due to ⁴T₁(⁴P)→⁴A₂(⁴F) and ⁴T₁(⁴P)→⁴T₂(⁴F) tetrahedral transitions of Co²⁺ ions, respectively. With the increasing content of cobalt ions in the glass matrix, the half width and intensity of these bands are observed to increase. The analysis of the results of these two spectra coupled with IR spectra has indicated that as the concentration of CoO is increased in the glass matrix, the tetrahedral occupancy of cobalt ions dominates over the octahedral occupancy and increase the rigidity of the glass network.     

Infrared to visible upconversion fluorescence in Yb,Tm:YAG single crystal

Absorption spectrum from 400 to 2000 nm and upconversion fluorescence spectra under 940 nm pumping of YAG single crystal codoped with 5 at.% Yb³⁺ and 4 at.% Tm³⁺ were studied at room temperature. The blue upconversion emission centered at 483 nm corresponds to the transition ¹G₄ → ³H₆, the emission band around 646 nm corresponds to the transition ¹G₄ → ³F₄ of Tm³⁺. Energy transfer from Yb³⁺ to Tm³⁺ is mainly nonradiative and the transfer efficiency was experimentally assessed. The line strengths, transition probabilities and radiative lifetimes of ¹G₄ level were calculated by using Judd-Ofelt theory. Gain coefficient calculated from spectra shows that the upconversion corresponding with transitions ¹G₄ → ³H₆ in YAG doped with Yb³⁺ and Tm³⁺ is potentially useful for blue light output.     

Characterization, EPR and luminescence studies of ZnAl2O4:Mn phosphors

ZnAl₂O₄:Mn green light emitting powder phosphors have been prepared by urea combustion technique involving furnace temperatures about 500 °C in a short time (<5 min). The prepared powders were characterized by X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectrometry and the surface area measurements by a Brunauer-Emmet-Teller (BET) adsorption isotherms. The EPR spectrum exhibits a resonance signal at g≈2.0, which shows a six-line hyperfine structure (hfs). From the EPR spectra the spin-Hamiltonian parameters have been evaluated at room temperature as well as at 110 K. EPR and photoluminescence (PL) studies revealed that manganese ions were present in divalent state and the site symmetry around Mn²⁺ ions is distorted tetrahedral. The spin concentration (N), the paramagnetic susceptibility (χ) and the zero-field splitting parameter (D) have been evaluated and discussed. The green emission at 511 nm in ZnAl₂O₄:Mn phosphor is assigned to a transition from the upper ⁴T₁→⁶A₁ ground state of Mn²⁺ ions.     

High Pressure effect on fluorescence lifetime τ for magnetic dipole 5D0→5F1 transitions in YAG:Eu3+

The fluorescence lifetime for magnetic dipole ⁵D₀→⁷F₁ transition in yttrium aluminum garnet doped with Eu³⁺ (YAG:Eu³⁺) crystal was studied under the pressure of up to 10.4?GPa at room temperature. The fluorescence lifetime τ (⁵D₀→⁷F₁ transition) slowly decreased with pressure. The pressure effect on τ (⁵D₀→⁷F₁ transition) was explained with a model which considered pressure effect on line position: inter-ionic distance, ion volume, molecular volume, ion polarizability, molecular polarizability, sample refractive index, and surrounding hydrostatic medium refractive index. The fluorescence lifetime τ calculated by the presented model was in close correspondence with the experimental values.     

Optical absorption and emission properties of Nd in TeO2-WO3 and TeO2-WO3-CdO glasses

Effects of WO₃ and CdO on the spectroscopic properties of Nd³⁺ doped tellurite glasses were investigated. The optical band gaps and Urbach energies of the samples were determined using the dependence of the absorption coefficient on the photon energy. The Urbach energies were found to vary from 0.18 to 0.25 eV as the WO₃ content in the binary glasses decreased from 20.0 to 10.0 mol% while the optical band gap of the same glasses did not show an appreciable dependence on the glass composition. Judd-Ofelt (Ω_t) parameters were calculated from the optical absorption spectra measured at room temperature. In all the glasses the J-O parameters follow the same trend as Ω₂>Ω₆>Ω₄. The J-O intensity parameters were used to compute the radiative properties such as the radiative transition probabilities (A_ed), branching ratios (β) and radiative lifetimes (τ_r) for all the possible fluorescence bands. The fluorescence spectra obtained upon 805.2 nm excitation exhibited an intense emission band centered at 1064 nm (⁴F_3/2→⁴I_11/2) and two weak bands at 910 nm (⁴F_3/2→⁴I_9/2), and 1340 nm (⁴F_3/2→⁴I_13/2). The stimulated emission cross-section for the 1064 nm emission was determined using the emission spectra. The highest gain bandwidth (σ_e×Δλ_P) was determined to be 155.4 for the 0.79TeO₂-0.15WO₃-0.05CdO ternary glass composition, which could be more useful as promising material for the design and development of fiber amplifiers and lasers.     

Confirmation of temperature independence in the fluorescence lifetime of the P0 → F2 transition in praseodymium-doped fluoride glass

The dependence of the fluorescence lifetime from the ³P₀ → ³F₂ transition in praseodymium-doped fluoride glass as a function of dopant concentration and temperature was investigated. It was found that the fluorescence lifetime at the concentration of 7000 ppm was constant with temperature, confirming the prediction of temperature independence in the lifetime for this transition in Pr³⁺-doped ZBLAN glass.     

Temperature-dependent fluorescence characteristics of an ytterbium-sensitized erbium-doped tellurite glass

In this article, the 1.5 μm emission spectra corresponding to the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ in tellurite glass are studied within the temperature from 8 to 300 K. The emission spectra of Er³⁺: ⁴I_13/2→⁴I_15/2 transition are also analyzed using a peak-fit routine, and an equivalent four-level system is proposed to estimate the stark splitting for the ⁴I_15/2 and ⁴I_13/2 levels of Er³⁺ in the tellurite glass. The results indicate that the ⁴I_13/2→⁴I_15/2 emission of Er³⁺ can exhibit a considerable broadening due to a significant enhance the peak a′, and b′ change, respectively, and the peaks of which are located at about 1507 and 1556 nm. A detailed study of temperature-dependent 1.5 μm emission spectra involving the change of the corresponding sub-bands shows that as the temperature decreases from 300 to 8 K, its line-shape becomes sharper and more intense (the full-width at half-maximum decreases from 59 to 38 nm). Temperature-dependent fluorescence intensities and the experimentally determined lifetimes are investigated; the results show that a decrease behavior of fluorescence intensities and lifetimes are observed for temperature from 8 to 300 K.     

Solvothermal synthesis and luminescence properties of Tb-doped gadolinium aluminum garnet

Different concentrations of Tb³⁺ ion-doped gadolinium aluminum garnet (GAG) nanophosphors have been synthesized by solvothermal reaction method and sintered at 1300 °C. The XRD patterns confirm that the GAG phosphors sintered at 1300 °C have a garnet structure with single cubic phase. The calculated crystallite size is about 92 nm. The SEM images of the phosphors show the spherical morphology agglomerated with many small particles. The luminescence properties of these phosphors have been carried out by the emission and excitation spectra along with lifetime measurements. The excitation spectra of GAG:Tb³⁺ phosphors consist of three broad bands due to the 4f⁸→4f⁷5d¹ transition and some sharp peaks due to the 4f⁸→4f⁸ transition. The emission spectra of the phosphors reveal two colors, such as blue due to ⁵D₃→⁷F_J transitions and green due to the ⁵D₄→⁷F_J transitions. The dynamics of the phosphors have been investigated by decay curves and the cross-relaxation process and is observed at 0.5 mol% Tb³⁺ concentration.