Optical spectroscopy and crystal-field strength of Cr^(3+) in various solid matrixes

The Cr^3＋：BeAl2O4 crystal, Cr^3＋：LiNbO3 crystal, and ZnO-Al2O3-SiO2 glass-ceramic were obtained by the Czochralski technique, Bridgman method, and melting processing, respectively. The optical absorption and emission spectra of the above Cr^3＋-incorporated solid-state materials were recorded. The technical parameters for growing high-quality Cr^3＋：BeAl2O4 and Cr^3＋：LINbO3 crystals were obtained. The results indicate that the optical absorption and fluorescence spectra of Cr^3＋ show quite a few differences in various matrixes. The sharp line emissions were observed in the Cr^3＋：BeAl2O4 and Cr^3＋：LiNbO3 crystals. The crystal-field parameters （Dq） for Cr^3＋. in different matrixes were calculated from their corresponding spectra. It is indicated that Cr^3＋：BeAl2O4 and Cr^3＋：LiNbO3 belong to the high-field site crystal, while the Cr^3＋ ZnO-Al2O3-SiO2 glass and glass-ceramic belong to the weak-field site crystal.

Growth and Optical Spectra of Zn∶Er∶LiNbO_3 Crystals Using Bridgman Method

The growth of LiNbO3 single crystal with Er^3＋ and Zn^2＋ co-doped using Bridgman method and its characteristic absorption spectra and fluorescence spectra were reported. Large-size crystals initially containing Zn^2＋ （3%） and Er^3＋ （0.6%） with good optical quality were obtained using optimized conditions such as a growth rate of 0.8- 1.5 mm·h^-1 and a temperature gradient of about 30 - 35℃·cm^-1 across the solid-liquid interface and the sealed platinum crucible. X-ray diffraction and differential thermal analysis （DTA） were used to characterize the crystals. The results indicate that the concentration of Er^3＋ ions in crystals, their absorption intensity, and their fluorescence intensity decrease from the bottom to the top in the crystals. However, for the upper part of the crystal, the up-conversion fluorescence intensity is higher than that of the lower part excited by an 800 or 970 nm pump. The effects of the crystal lattice, their structural defect and their effective segregation of Er^3＋ ions were discussed with respect to the variations of the up-conversion fluorescence intensity.

2 μm mid-infrared optical spectra of Tm3+-doped germanium gallate glasses

Glasses with the composition of 65GeO212Ga2O3-10BaO-8Li2O-5La2O3(molar ratio) doped with 1.526 wt.%, 3.006 wt.%, 5.836 wt.%, 11.028 wt.%, and 15.678 wt.% Tm2O3, respectively, were fabricated by conventional melting method. According to the absorption spectra and the Judd-Ofelt theory, the J-O strength parameters (Ω2,Ω4, Ω6) were calculated, with which the radiative transition probabilities,branching ratios and radiative lifetimes were obtained. The infrared emission spectra (with 808 nm LD excitation) at～1.47 and～1.8 μm of various concentrations of Tm3+-doped glasses were studied. The emission intensity at～1.8 μm reached to the maximum when the Tm2O3-doping concentration was near to be～3.006 wt.% (1.0 mol.%), and then decreased as doping concentration increased further. The mechanism of the fluorescence intensity change was explained with the cross-relaxation effect and the concentration quenching effect of Tm3+. Meanwhile, according to McCumber theory, the absorption and emission cross-sections corresponding to the 3F4→3H6 transitions of Tm3+ at 1.8 μm was obtained. For Tm3+-doped germanate glasses, the maximum emission cross-section reached a value higher than that re-ported for fluorozircoaluminate glasses. It is expected to be a favorable candidate host for～2.0 μm mid-inflated laser because the glass shows favorable optical spectra.

Optical Spectroscopy of Er^(3+) and Er^(3+)/Yb^(3+)Co-doped Bi_2O_3-GeO_2-B_2O_3-ZnO Glasses

The （60 - x）Bi2O3 - xGeO2-30B2O3-10ZnO （x = 5, 10, 20, 30 molar percent） glasses doped with Er^3＋ and Er^3＋/Yb^3＋ were fabricated using the melting method. The thermal stability of the glasses was studied with their DTA curves. The results show that the difference between the glass transition temperature and the crystallization onset temperature increases with the increase of GeO2 content, indicating that the thermal stability of the glass has become better. The absorption spectra were recorded and the stimulated emission cross sections were calculated using the McCumber theory. The Ω2, O4, and Ω6 parameters,the transition probability, the radiative lifetime, and the fluorescence branch ratio of Er^3＋ for optical transition were calculated from their absorption spectra in terms of reduced matrix U^（t）（λ = 2, 4, 6） character for optical transitions. The infrared emission of Er^3＋ was measured upon excitation with 970 nm light and the full width at half-maximum （FWHM） was estimated from the emission spectra. The pumping efficiency and the intensity of the emission at the 1.54 μm band of Er^3＋ were enhanced considerably by co-doping Yb^3＋ .

Gain properties of germanate glasses singly doped with Tm^(3+) and Ho^(3+) ions

Two kinds of germanate glasses singly doped with the ion concentration of 2.0mol.%Tm3＋ and 2.0mol.%Ho3＋, respectively, were prepared.According to McCumber theory, the absorption and stimulated emission cross-sections corresponding to the 3H6←→3F4 transitions of Tm3＋（at 1.8 μm） and the 5I8←→5I7 transitions of Ho3＋（at 2.0 μm） were obtained, and respective gain cross-section spectra were also computed as a function of population inversion according to absorption and emission cross-sections and the ion concentrations.For Tm3＋-doped germanate glasses, the maximum of the absorption, emission, and gain cross-sections reached a value higher than those reported for fluorozirconate, fluoride, and oxyfluoride glasses.For Ho3＋-doped germanate glasses, the maximum of absorption, emission, and gain cross-sections reached a value higher than that reported for fluorozircoaluminate glasses.Hence, these Tm3＋-doped and Ho3＋-doped germanate glasses exhibited an advantage for application in mid-infrared lasers at about 1.8 and 2.0 μm wavelength.

Fluorescence properties of divalent and trivalent europium ions in CdWO_4 single crystals grown by the Bridgman method

Optical absorption,excitation,and fluorescence were investigated in Eu ion-doped CdWO4 single crystal grown by a modified Bridgman method.The results indicate that Eu^2＋ and Eu^3＋ ions coexist in CdWO4 crystal and an energy transfer occurs between these Eu^2＋ and Eu^3＋ ions.When the crystal is excited by 266-nm light,the energy corresponding to the 4f65d to 8S7/2 transition of Eu^2＋ ions results in the excitation of the Eu^3＋ ions to the 5DJ level.The effect on fluorescence of annealing in oxygen at various temperatures was investigated.The excitation intensity of Eu^2＋ ions at 266 nm decreases as annealing temperature increases from 300 K to 1073 K,but it remains at a certain equilibrium level when the annealing temperature is further increased.

Optical Spectroscopy of Er^(3+), Er^(3+)/Yb^(3+) Co-doped Bi_2O_3-GeO_2-B_2O_3-ZnO Glasses

The （60 - x） Bi2O3-xGeO2-30B2O3-10ZnO （x = 5, 10, 20, 30 molar percent） glasses doped with Er^3＋ and Er^3＋/Yb^3＋ were fabricated by melting method. The thermal stability of the glasses was studied by their DTA curves. The results indicate that the difference between the glass transition temperature and the crystallization onset temperature increase as increase of GeO2 content, indicating that the thermal stability of the glass becomes better. The absorption spectra were recorded. The stimulated emission cross sections were calculated by McCumber theory. The Ω2, Ω4, and Ω6 parameters, transition probability, radiative lifetime, fluorescence branch ratio of Er^3＋ for optical transition were calculated from their absorption spectra in terms of reduced matrix U^（1）（λ = 2, 4, 6） character for optical transitions. The infrared emission was measured by excitation with 970 nm light and the FWHM was estimated from their emission spectra. The pumping efficiency and the intensity of emission at the band of 1.54 μm are enhanced greatly by addition of Y2O3.

Optimum fluorescence emission around 1.8μm for LiYF_4 single crystals of various Tm^(3+)-doping concentrations

In this paper, optical spectra of LiYF4 single crystals doped with Tm3＋ ions of various concentrations are reported. The emission intensity at 1.8 ktm first increases with increasing Tm3＋ concentration, and reaches a maximum value when the concentration of Tm3＋ is about 1.28 mol%, then it decreases rapidly as the concentration of Tm3＋ further increases to 3.49 mol%. The emission lifetime at 1.8 p.m also shows a similar tendency to the emission intensity. The maximum lifetime of 1.8 μm is measured to be 17.68 ms for the sample doped with Tm3＋ of 1.28 mol%. The emission cross section of 3F4 level is calculated. The maximum reaches 3.76 × 10 -21 cm2 at 1909 nm. The cross relaxation （3H6, 3H4 →3 F4, 3F4） between Tm3＋ ions and the concentration quenching effect are mainly attributed to the change of emission with Tm3＋ concentration. The largest quantum efficiency between Tm3＋ ions is estimated to be ,-147% from the measured lifetime and calculated radiative lifetime. All the results suggest that the Tm3＋/LiYF4 single crystal may have potential applications in 2 μm mid-infrared lasers.

The effects of Er^(3+) ion concentration on 2.0-μm emission performance in Ho^(3+)/Tm^(3+) co-doped Na_(5)Y_(9)F_(32) single crystal under 800-nm excitation

Na_(5)Y_(9)F_(32) single crystals doped with ~0.8-mol% Ho^(3+),~1-mol% Tm^(3+),and various Er^(3+) ion concentrations were prepared by a modified Bridgman method.The effects of Er^(3+)ion concentration on 2.0-μm emission excited by an800-nm laser diode were investigated with the help of their spectroscopic properties.The intensity of 2.0-μm emission reached to maximum when the Er^(3+) ion concentration was ~1 mol%.The energy transfer mechanisms between Er^(3+),Ho^(3+),and Tm^(3+) ions were identified from the change of the absorption spectra,the emission spectra,and the measured decay curves.The maximum 2.0-μm emission cross section of the Er^(3+)/Ho^(3+)/Tm^(3+)tri-doped Na_(5)Y_(9)F_(32) single crystal reached 5.26 × 10^(-21) cm^(2).The gain cross section spectra were calculated according to the absorption and emission cross section spectra.The cross section for ~2.0-μm emission became a positive gain once the inversion level of population was reached 30%.The energy transfer efficiency was further increased by 11.81% through the incorporation of Er^(3+) ion into Ho^(3+)/Tm^(3+) system estimated from the measured lifetimes of Ho^(3+)/Tm^(3+)-and Er^(3+)/Ho^(3+)/Tm^(3+)-doped Na_(5)Y_(9)F_(32)single crystals.The present results illustrated that the Er^(3+)/Ho^(3+)/Tm^(3+)tri-doped Na_(5)Y_(9)F_(32) single crystals can be used as promising candidate for 2.0-μm laser.

Luminescent characteristics of Tm^(3+)/Tb^(3+)/Eu^(3+) tri-doped Na_(5)Y_(9)F_(32) single crystals for white emission with high thermal stability

By using an improved Bridgman method,0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/y mol%Eu^(3+)(y=0,0.4,0.6,0.8)doped Na_(5)Y_(9)F_(32)single crystals were prepared.The x-ray diffraction,excitation spectra,emission spectra and fluorescence decay curves were used to explore the crystal structure and optical performance of the obtained samples.When excited by 362 nm light,the cool white emission was realized by Na_(5)Y_(9)F_(32)single crystal triply-doped with 0.3 mol%Tm^(3+)/0.6 mol%Tb^(3+)/0.8 mol%Eu^(3+),in which the Commission Internationale de l’Eclairage(CIE)chromaticity coordinate was(0.2995,0.3298)and the correlated color temperature(CCT)was 6586 K.The integrated normalized emission intensity of the tridoped single crystal at 448 K could keep 62%of that at 298 K.The internal quantum yield(QY)was calculated to be~15.16%by integrating spheres.These results suggested that the single crystals tri-doped with Tm^(3+),Tb^(3+)and Eu^(3+)ions have a promising potential application for white light-emitting diodes(w-LEDs).

Luminescent properties of Ce^(3+)-doped transparent oxyfluoride glass ceramics containing BaGdF＿5 nanocrystals

The transparent oxyfluoride glass ceramics containing Ba Gd F5 nanocrystals were prepared with a composition of 42 Si O2-12Na2O-16Al2O3-24 Ba F2-4Gd2O3-2Ce F3（mol.%） by thermal treatment technology. The typical DSC curve, X-ray diffraction（XRD） and transmission electron microscopy（TEM） patterns were measured. The transmission spectra and luminescent properties were investigated. The decay times of the Gd^3＋ ions at 312 nm excited with 275 nm for the Ce^3＋ ions doped glass and glass ceramics specimens and the energy transfer process between Gd^3＋ ions and Ce^3＋ ions were also studied. The XRD analysis and the TEM images confirmed the generation of the spherical Ba Gd F5 nanocrystals. Compared with the PG specimen, the intensity of the luminescence spectra of the glass ceramics specimens was apparently enhanced with the heat treatment temperature increasing, and a blue shift in the excitation spectra and the emission spectra of glass ceramics specimens was obviously observed. In the fluorescence decay curves of the Gd^3＋ ions, it could be obviously observed that the fluorescent intensity decays in the Ce^3＋ ions doped glass and glass ceramics specimens decreased rapidly with the increase of the heat treatment temperature. In addition, the energy transfer efficiency from Gd3＋ions to Ce^3＋ ions was also calculated.

Near-white light-emitting Dy^(3+)-doped transparent glass ceramics containing Ba_2LaF_7 nanocrystals

Glass ceramics Ba2LaFT：xDy3＋ are obtained through the conventional melt-quenching technique, and their lu- minescent properties are investigated. Under 350 nm excitation, the emission spectra consists of a strong blue- yellow band as well as a weak red emission centered at 660 nm, which are attributed to the 4F9/2 →6H15/2, 4F9/2→6H13/2 and 4F9/2 → 6Hll/2 transitions of the Dy3＋ ion, respectively. The corresponding Commission Internationale de L＇Eclairage （CIE） chromaticity coordinate for a sample of 2 mol.% Dy203 after being heat-treated at 690℃ is （0.313, 0.328）. It is concluded that the formed materials may have the possibility of applications for white light-emitting diodes （LEDs）.

Preparation and optical spectroscopy of phosphate glasses containing divalent europium ions

P2O5.BaO.Na2O.K2O glasses doped with various content of Eu2O3 were prepared using high temperature melting method, and the Eu2+ ions in the phosphate glasses were obtained with the aid of the reductive action of silicon powder. The fabricating conditions, fluorescence, excitation spectra of the glasses were then studied. The glasses containing europium show a broad emission band at 450 nm and sharp bands from 580 to 650 nm, and the co-existence of Eu2+ and Eu3+ is identified. Also, a good glass with a dominant proportion and large quantity of Eu2+ ions can be obtained by the reductive action of silicon powder and proper processing.

Photoluminescence properties of Tm^(3+)/Tb^(3+)/Sm^(3+) tri-doped Na_(5)Y_(9)F_(32) single crystal with high thermal stability for white light-emitting diodes

A novel Tm^(3+)/Tb^(3+)/Sm^(3+)tri-doped Na_(5)Y_(9)F_(32)single crystal was synthesized by a modified Bridgman method for the propose of white light emitting diodes.The fluorescence spectra of various Sm^(3+)ion concentrations and fixed 0.4 mol%Tm^(3+)and 0.5 mol%Tb^(3+)were measured and studied systematically excited by near-ultraviolet light of 355 nm.The Sm3+ion concentration takes apparent effect on the relative intensity of peaks in the visible region and the color coordinate combining from these emission bands.A near pure white light emission with color coordinates(0.3295,0.3057)and color temperature(5657 K)can be obtained when the concentrations of Tm^(3+),Tb^(3+)and Sm^(3+)ions are 0.4 mol%,0.5 mol%and 0.8 mol%,respectively.Furthermore,the practical down-conversion internal quantum yield was measured by integrating spheres at about 14.39%.The tri-doped Na_(5)Y_(9)F_(32)single crystal shows a high thermal stability inferring from the temperature dependent emission in which the integrated emission intensities are reduced only by^3%with the increase of temperature from 280 to 450 K.The present results demonstrate that the Tm^(3+)/Tb^(3+)/Sm^(3+)tri-doped Na_(5)Y_(9)F_(32)single crystal may provide a promising candidate for white light-emitting diodes,luminescent materials and fluorescent display devices.

Preparation and characterization of Y_3Al_5O_(12):Ln(Ln=Eu,Ce) phosphor powders by ultrasonic atomization and co-precipitation process

A novel technique for YAG:Ln(Ln=Eu,Ce) phosphor powder synthesis with a nanocrystalline structure was developed.Nanocrystalline YAG:Ln powder was prepared by an ultrasonic atomization and co-precipitation method using a mixture solution of ammonium hydroxide(NH3·H2O) and ammonium hydrogen carbonate(NH4HCO3) as precipitant.The as-prepared nano-powders were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),and fluorescence spectrometer.The obtained phosphor powders were homogenous and in size of 50-70 nm.The results demonstrated that by using ultrasonic atomization and co-precipitation process,we could synthesize a good quality YAG:Ln(Ln=Eu,Ce) phosphor powder that had many potential applications.

White light emission from Dy^(3+)-doped LiLuF_4 single crystal grown by Bridgman method

Lithium lutetium fluoride(LiLuF4) single crystals doped with different Dy3+ ion concentrations were grown by Bridgman method. The Judd-Ofelt(J-O) strength parameters(Ω2, Ω4, Ω6) of Dy3+ in LiLuF4 crystal are calculated according to the measured absorption spectra and the J-O theory, by which the asymmetry of the Dy3+:LiLuF4 single crystal and the possibility of attaining stimulated emission from 4F9/2 level are analyzed. The capability of the Dy3+:LiLuF4 crystal in generating white light by simultaneous blue and yellow emissions under excitation with ultraviolet light is produced. The effects of excitation wavelength and doping concentration on chromaticity coordinates and photoluminescence intensity are also investigated. Favorable CIE coordinates, x=0.319 3 and y=0.349 3, can be obtained for Dy3+ ion in 2.701% molar doping concentration under excitation of 350 nm.

Luminescence of Tb^(3+)/Eu^(3+) codoped LiYF_4 single crystals under UV excitation for white-light LEDs

The absorption spectra, excitation spectra, and emission spectra of Tb3＋/Eu3＋ ions in LiYF4 single crystals synthesized by an improved Bridgman method are measured. The emission spectra of several bands, mainly located at blue^487 nm （Tb：5D4→7F6）, yellowish green ~542 nm （Tb：SD4→ 7F5）, and red ~611 nm （Eu：SD0 → 7F2） wavelengths, are observed under excitation by UV light. An ideal white light emission as a result of simultaneous combination of these emissions can be obtained from 1.11 mol%Tb3＋ and 0.9 mol% Eu3＋ co-doped LiYF4 single crystals with chromaticity coordinates of x = 0.3242, y = 0.3389, color temperature Tc = 5878 K, color rendering index Ra = 77, and color quality scale Qa = 75 under excitation of 384 nm light. The chromaticity coordinate, color rendering index, and color quality scale can be modified by the change of the concentration of rare-earth dopants and the excitation wavelength.

Optical spectra and local structure of Eu^(3+) ions doped in Nb_2O_5-La_2O_3-B_2O_3-BaO glasses

The xNb2O5-（15-x）La2O3-40B2O3-45BaO （x = 5, 7.5, 12.5 mol%） glasses doped with Eu^3＋ ions in 1 mol% are fabricated by the melting method. The Fourier transform infrared （FTIR） spectra, phonon sideband spectra, emission and excitation spectra of the glasses are measured. The crystal field parameter and coordination number of Eu^3＋ ions in the glasses are obtained according to the splitting of their ^5D0 - ^7F1 levels. The intensity parameters Ω2 and Ω4 of Eu^3＋ ions for optical transition are calculated from their emission spectra in terms of reduced matrix U^（t） （λ= 2, 4, 6） character for optical transitions. The results indicate that the intensity parameters Ω2 and Ω4 increase with the increase of Nb2O5 content, suggesting that the symmetry becomes lower, the band of Eu and O atoms becomes stronger and the covalence increases with the increase of Nb2O5 content.

Efficient up-conversion Yb3+, Er3+ co-doped Na5Lu9F32 single crystal for photovoltaic application under solar cell spectrum excitation

Yb^3+/Er^3+co-doped Na5Lu9F32 single crystals used as a spectral up-converter to improve the power conversion efficiency of perovskite solar cells are prepared via an improved Bridgman approach. Green and red up-conversion(UC) emissions under the excitation of near-infrared(NIR) bands of 900–1000 nm and1400–1600 nm can be observed. The effectiveness of the prepared materials as a spectral converter is verified by the enhancement of power conversion efficiency of perovskite solar cells. The sample with a UC layer is 15.5%more efficient in converting sunlight to electricity compared to the UC layer-free sample due to the absorption of sunlight in the NIR range. The results suggest the synthesized Yb^3+/Er^3+co-doped Na5Lu9F32 single crystals are suitable for enhancing the performance of perovskite solar cells.

Dy^(3+)-doped LiYF_4 crystals for UV-excited white light-emitting diodes

A Dy3＋-doped LiYF4 single crystal capable of generating white light by simultaneous blue and yellow light emission of phosphorescent centers is produced. Chromaticity coordinates and photoluminescence intensity vary with excitation wavelength. Under 350, 365, and 388 nm excitation, the crystal shows excellent white light emission. The most efficient wavelength for white light is 388 nm. The CIE coordina.tes are x=0.316 and y =0.321, and the color temperature （Tc） is 6 368 K. These results indicate that the studied crystal is a potential candidate for ultraviolet light-excited white light-emitting diodes.