Enhanced visible green and 1.5 μm radiative emission of Er~(3+) ions in Li_2O-PbO-Al_2O_3-B_2O_3 glasses for photonic applications

A series of Er~(3+) ions doped lithium lead alumino borate(LiPbAlB) glasses were synthesized via melt quench method and their structural,physical and optical properties were studied.Judd-Ofelt theory in correlation with the emission and absorption profiles was performed for the measurement of various radiative parameters for different transitions of Er~(3+) doped glasses.The as-prepared glasses show deep green(550 nm) as well as NIR(1532 nm) emission at 380 and 980 nm excitation wavelengths,respectively.The intensity of emission spectra increases with Er~(3+) ions concentration up to 1.5 mol% and beyond quenching is observed.The Dexter theory applied to the emission profiles reveals the interaction between Er~(3+)ions as dipole-dipole in nature.CIE color coordinates are found to fall in the green region of the visible spectrum.It is observed that 1.5 mol% of Er~(3+) ions concentration is optimum to exhibit the maximum quantum efficiency,branching ratios,gain bandwidth,emission cross-section,gain crosssection and aptly suitable for visible and NIR photonic applications.     

Highly sensitive up-conversion phosphor for optical thermometry:CaLaAl_3O_7:Er~(3+)/Yb~(3+)

Herein, we reported Er~(3+)/Yb~(3+) co-doped CaLaAl_3O_7 up-conversion phosphors synthesized via solid state reaction, which was further explored as a new optical thermometry. The luminescent properties of Er~(3+) or Er~(3+)/Yb~(3+) doped CaLaAl_3O_7 phosphor was studied in detail. The two-photon process for the green emissions of Er~(3+) were confirmed by the power-dependent luminescence. The up-conversion optical temperature sensing performances of the Er~(3+)/Yb~(3+)-codoped CaLaAl_3O_7 phosphor were investigated based on the FIR technique. The maximum sensitivity of this phosphor can reach about 0.00345 K~(-1) at 453 K, which reveals this phosphor can be a promising candidate for optical thermometry devices.     

Optical Properties and Spectroscopic Parameters of Sm （DBM）3 Doped Polymethyl Methacrylate

Optical absorption spectra of Sm(DBM)3 doped PMMA (polymethyl methacrylate) in near infrared and visible region are presented. The energy levels were assigned and analyzed in terms of the free-ion Hamiltonian model. Energy levels and reduced matrix elements calculations were carried out using the complete 198 SLJ basis sets for the 4f^5 configuration. Judd-Ofelt parameters were evaluated and used to predict the radiative properties of the sample. The theoretical and experimental values for radiative lifetimes and branching ratios were discussed.     

Synergistic effect of crystal structure and concentration quenching on photoluminescence of Er~(3+) doped upconversion nanocrystals

YbF_(2.357), YbF_3, Ba_2 YbF_7, and Ba _2 upconversion nanocrystals doped with emitter Er~(3+) ion were synthesized in the same solvent system just with changing the molar ratio of Ba~(2+) to Yb~(3+) in the precursor, which corresponed to the crystal phases of rhombohedral, orthorhombic, tetragonal, and cubic, respectively. All the samples emitted both 660 nm red light and 543/523 nm green light which originated from Er~(3+)-4f~n electronic transitions ~4F_(9/2)-~4I_(15/2) and ~4S_(3/2)/~2H_(11/2)-~4I_(15/2), respectively. It was worth mentioning that YbF 3:Er~(3+), Ba_2 YbF_7:Er~(3+), and BaF_2:Er~(3+) could emit dazzlingly bright light even under the excitation of a 980 nm CW laser with output power of 0.1 W. Upconversion emission mechanism analysis indicated that the intensity ratio of red to green light highly depended on the synergistic effect of crystal structure, concentration quenching, and particle size, but were not sensitive to crystallinity as previously reported for NaL nF_4(Ln=lanthanide).     

Synthesis and characterization of NaYF_4:Yb~(3+),Er~(3+)@silica-N=folic acid nanocomplex for bioimaginable detecting MCF-7 breast cancer cells

Upconversion nanophosphors are new promising nanomaterials to be used as biolabels for detection and imaging of cancer cells.These nanophosphors absorb long-wavelength excitation radiation in the infrared or near infrared region and emit shorter wavelength,higher energy radiation from ultraviolet to infrared.In this paper,we studied the hydrothermal method and optical properties of the functionalized NaYF_4:Yb~(3+),Er~(3+)for biomedical application.After synthesis,these NaYF_4:Yb~(3+),Er~(3+)nanophosphors were functionalized with aminosilanes and folic acid.Folic acid binds to the folate receptor on the surface of MCF-7 breast cancer cells and this binding promotes internalization of the nanophosphors via endocytosis.The sizes of the functionalized NaYF_4:Yb~(3+),Er~(3+)@silica-N=FA(folic acid) nanophosphors can be controlled with length of the rod about 300-800 nm and diameter of the rod about 100-200 nm.Phase structure of NaYF_4:Yb~(3+),Er~(3+)is in hexagonal crystal system.The photo luminescence(PL) spectra of the functionalized NaYF_4:Yb~(3+),Er~(3+)@silica-N=FA nanophosphors were measured.These nanophosphors emit in red color with the strongest band at 650 nm under 980 nm excitation.This result can provide NaYF_4:Er~(3+),Yb~(3+)@silica-N=FA complex for developing fluorescence label and image tool in cancer biology and medicine.     

Broadband Cr~(3+)-sensitized upconversion luminescence of LiScSi_2O_6:Cr~(3+)/Er~(3+)

Broadband sensitization is an effective strategy to enhance the upconversion luminescence(UCL) of lanthanide ions.Herein,novel UC materials LiScSi_2 O_6:Cr~(3+)/Er~(3+)(LSS:Cr~(3+)/Er~(3+)) were synthesized by high-temperature solid state reaction and their luminescent properties were investigated.LSS:Cr~(3+)/Er~(3+)has the broadband absorption in the spectral range of 600-800 nm,and meanwhile shows green UC emissions of Er~(3+)upon pumping Cr~(3+) by the 690 nm laser.The UCL of LSS:Cr~(3+)/Er~(3+)belongs to the twophoton process and is attributed to the energy transfer upconversion mechanism.The effects of the Cr~(3+)and Er~(3+)concentration as well as the Yb~(3+)introduction were also studied.LSS:Cr~(3+)/Yb~(3+)/Er~(3+) exhibits the interesting dual-mode UCL,capable of generating the UCL of Cr~(3+) upon pumping Yb~(3+)ions and the UCL of upon pumping Cr~(3+) ions.This research might promote the development of novel broadband Cr~(3+)-sensitized UC materials.     

Spectroscopic investigations on Dy3+ ions doped zinc lead alumino borate glasses for photonic device applications

This paper presents the structural, optical absorption, photoluminescence (PL) and decay spectral properties of Dy~(3+)ions doped zinc lead alumino borate (ZPAB) glasses to elucidate their possible usage in photonic devices such as w-LEDs and lasers. A broad hump shown by the XRD spectrum recorded for an un-doped ZPAB glass confirms its non-crystalline nature. The Judd-Ofelt (J-O) intensity parameter evaluated from the measured oscillator strengths of the absorption spectral features were used to estimate various radiative parameters and also to understand the nature of bonding between Dy~(3+)ions and oxygen ligands. Under 350 nm excitation, the as-prepared glasses are exhibiting two emission bands~4F_(9/2)→~6H_(15/2)(blue),and~4F_(9/2)→~6H_(13/2)(yellow) at 483 and 575 nm,respectively. From the PL spectra,the Y/B ratio values, CIE chromaticity color coordinates and color correlated temperature (CCT) were evaluated. The experimental lifetimes measured from the decay profiles are decreasing with increase in Dy~(3+)ions concentration in these glasses which may be attributed to the cross-relaxation and nonradiative multiphonon relaxation process. Decay profiles observed for higher concentration were well fitted to Inokuti-Hirayama (I-H) model to understand the energy transfer process and subsequent decrease in experimental lifetimes. The higher values of radiative parameters, emission cross-sections,quantum efficiency, optical gain and gain band width suggest the suitability of 0.5 mol%of Dy~(3+) ions in these ZPAB glasses for the photonic device application.     

Investigation on 1.07 μm laser emission in Nd~（3＋）-doped sodium fluoroborate glasses

Spectroscopic and fluorescence properties of Nd 3+ ions in sodium fluoroborate(SFB) glasses were prepared and characterized through optical absorption,emission and decay measurements.The energy level analysis was carried out using free-ion Hamiltonian model.Experimental oscillator strengths were determined by measuring the area encompassed by the absorption peaks recorded for 1.0 mol.% Nd 3+-doped glasses.The Judd-Ofelt parameters(2,4,6) were used to evaluate the laser characteristic parameters such as radiative transition probability(A R),radiative decay time(τ R),fluorescence branching ratio(β R) and stimulated emission cross-section(σ e) for the 4 F 3/2 metastable state.The fluorescence spectra for different concentrations of Nd 3+ ions were recorded by exciting the samples at 514.5 nm Ar + ion laser.     

Multi－diffused Reflection Spectroscopy of Rare Earths Doped LaOCl Powder Samples and the Calculation of Quantum Efficiency

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Preparation and upconversion luminescence modification of YbPO_4:Er~(3+) inverse opal heterostructure

Photonic crystal heterostructures composed of YbPO_4:Er~(3+) inverse opal and polystyrene opal were prepared via a template-assisted process, which exhibited two photonic band gaps. The microstructure,phase and optical properties of photonic crystal heterostructures were investigated by x-ray diffraction,scanning electron microscopy, fluorescence spectroscopy, absorption spectroscopy, fluorescence lifetime,etc. The upconversion emission suppression caused by single photonic band gap from the following YbPO_4:Er~(3+) inverse opal or the upper opal was observed. The upconversion luminescence was strongly suppressed due to the two photonic band gap overlapping effect caused by the following YbPO_4:Er~(3+) inverse opal or the upper opal. The modified mechanisms of upconversion luminescence were discussed by the upconversion luminescence lifetime of YbPO_4:Er~(3+) photonic crystal heterostructures. The results demonstrated the modified upconversion luminescence is attributed to the photon trapping caused by Bragg reflection of photonic crystal heterostructures.     

Crystal-field analyses for trivalent lanthanide ions in LiYF_4

Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln~(3+) in LiYF_4 were systematically analyzed. The results revealed that the regular variation trends of the major parameters at relatively low site symmetry still existed. The g factors of ground states were calculated using the parameters obtained from least-squares fitting. The results for Ce~(3+), Nd~(3+), Sm~(3+), Dy~(3+) and Yb~(3+) were in good agreement with experiment, while those of Er~(3+) deviated from experiment dramatically. Further study showed that the g factors depended strongly on B_4~6, and a slightly different B_4~6 value of -580cm~(-1) led to g factors agreeing well with the experimental values.     

Microcapsules containing ionic liquid [A336][P507] for La~(3+)/Sm~(3+)/Er~(3+)recovery from dilute aqueous solution

The efficacy of polysulfone microcapsules encapsulating ionic liquid [trialkylmethylammonium][di(2-ethylhelxyl) orthophosphinate]([A336][P507]) for the extraction of La~(3+), Sm~(3+) and Er~(3+) from dilute aqueous solutions was investigated. Microcapsules were synthesized using coaxial microfluidic method, and subsequently encapsulated with extractant [A336][P507]. The kinetics data were fitted well by pseudo-second-order equation and Crank model, and the kinetics parameters were evaluated. The extraction rate had the order of Er~(3+)Sm~(3+)La~(3+). The isotherm data were analyzed by Langmuir model and shifted Langmuir model. The extraction capacities of La~(3+), Sm~(3+) and Er~(3+) were 58.4, 56.6 and 81.7 mg/g, respectively. The dependency of stripping performance on HNO3 concentration was measured. The regeneration of microcapsules was evaluated using cycling extraction experiments.     

Influence of In3＋ ions concentration on spectroscopic properties of Ho：LiNbO3 crystals

In:Ho:LiNbO3 crystals doped with various concentrations of In3+(0, 1 mol.%, 3 mol.%, 5 mol.%), fixed concentrations of Ho3+ (1 mol.%) were grown by Czochralski method. The X-ray powder diffraction, infrared and UV-visible absorption spectra were measured and modified. Judd-Ofelt approach was employed to study the effect of In doping on spectroscopic properties of Ho:LiNbO3 crystals. In concentrations in crystals were analyzed by an inductively coupled plasma optical emission spectrometry (ICP-OE/MS). For In (3 mol.%):Ho (1 mol.%):LiNbO3 crystal, the obtained intensity parameters were: Ω2=9.6563, Ω4=4.2195, Ω6=14.1526. The results showed that the Ω2 and Ω6 parameters increased with the increase of In3+ concentration. When the In doping concentration was up to 5 mol.%, Ω2 and Ω6 suddenly decreased. In2O3 incorporation had a strong effect on the radiative lifetime, but had less influence on fluorescence branching ratios. The effective distribution coefficient of In3+ in In:Ho:LiNbO3 crystals was less than 1 and increased with increasing concentration of In3+ in the melt.     

Sub-10 nm lanthanide-doped SrFCl nanoprobes:Controlled synthesis,optical properties and bioimaging

Alkaline-earth dihalide nanocrystals(NCs) such as SrFCl, owing to their high chemical stability and low phonon energy, are excellent host materials for lanthanide(Ln~(3+)) doping to achieve desirable optical properties for various bioapplications, Herein, we report a novel strategy for the synthesis of sub-10 nm Ln~(3+)-doped SrFCl NCs with efficient upconverting and downshifting luminescence through a facile onestep hot-injection method. Utilizing the temperature-dependent upconverting luminescence(UCL) from the thermally coupled ~2H_(11/2) and ~4S_(3/2) levels of Er~(3+), we showed the potential of SrFCl:Yb,Er NCs as sensitive UCL nanoprobes for non-contact thermal sensing with a maximum detection sensitivity of 0.0066 K~(-1), which is among the highest values for thermal sensing based on Er~(3+)-activated UCL nanoprobes. Furthermore, by employing the intense downshifting luminescence from Tb~(3+) and Eu~(3+), we demonstrated the successful use of biotinylated SrFCl:Ce,Tb and SrFCl:Eu~(3+) nanoprobes for biotin receptor-targeted cancer cell imaging, thus revealing the great promise of SrFCl:Ln~(3+) nanoprobes for versatile bioapplications.     

Spectroscopic Properties of Nd^3＋ -Doped High Silica Glass Prepared by Sintering Porous Glass

A new kind of Nd^3＋-doped high silica glass （SiO2 〉 96% （mass fraction）） was obtained by sintering porous glass impregnated with Nd^3 ＋ ions. The absorption and luminescence properties of high silica glass doped with different Nd^3 ＋ concentrations were studied. The intensity parameters Ωt （t = 2, 4, 6）, spontaneous emission probability, fluorescence lifetime, radiative quantum efficiency, fluorescence branching ratio, and stimulated emission cross section were calculated using the Judd-Ofelt theory. The optimal Nd^3＋ concentration in high silica glass was 0.27% （mole fraction） because of its high quantum efficiency and emission intensity. By comparing the spectroscopic parameters with other Nd^3 ＋- doped oxide glasses and commercial silicate glasses, the Nd^3 ＋ -doped high silica glasses are likely to be a promising material used for high power and high repetition rate lasers.     

Spectroscopic Properties and Judd-Ofelt Theory Analysis of Er^3＋-Doped Heavy Metal Oxyfluoride Silicate Glass

Er^3 -doped heavy metal oxyfluoride silicate glass was fabricated and characterized, and the absorption spectrum and fluorescence spectrum of the glass were studied. The Judd-Ofelt intensity parameters Ωt(t=2, 4, 6), spontaneous transition probability, fluorescence branching ratio and radiative lifetime of each energy levels for Er^3 were calculated by Judd-Ofelt theory, and stimulated emission cross-section of ^4I13/2→^4I15/2 transition was calculated by McCumber theory. The results show that fluorescence full width at half maximum and stimulated emission cross-section of Er^3 -doped heavy metal oxyfluoride silicate glass are broad and large, respectively. Compared with other host glasses, the gain bandwidth property of Er^3 -doped heavy metal oxyfluoride silicate glass is close to those of tellurite and bismuth glasses, and has advantage over those of silicate, phosphate and germante glasses.     

Up-Conversion Emission of Er3+ Ions in Yb3+ Sensitized Oxide Crystals

Most of the up-conversion lasers operated at room temperature are realized with heavy metal fluorides, In this paper the Judd-Ofelt parameters Ωλ ( λ = 2,4,6 ) were calculated for Er3+ ions in Yb3 + sensitized LiNbO3 and YVO4 crystals at room temperature, together with the radiative transition probabilities, non-radiative transition probabilities and resonant transition probabilities of Er3+ ions. Taking into account the energy transfer from Yb3 + to Er3 +, the rate equations are given for Er3 + ions. We obtained from a solution of the rate equations that Yb3 + sensitized YVO4 crystal is more efficient than Yb3 + sensitized LiNbO3 crystal in the up-conversion of 550 nm of Er3+ emission, which is consistent with our observation.     

Ce(DBM)3Phen doped poly(methyl methacrylate) for three-dimensional multilayered optical memory by femtosecond laser

The formation of submicrometer voids within Ce(DBM)3Phen doped poly(methyl methacrylate)(PMMA) was reported under multiphoton absorption excited by an infrared laser beam. The absorption spectra, photoluminescence and electron spin resonance (ESR) spectra before and after femtosecond laser irradiation were discussed. An ultrashort-pulsed laser beam with a pulse width of 200 femtosecond at a wavelength of 800 nm was focused into doped PMMA. The large changes in refractive index and the fluorescence associated with a void allowed conventional optical microscopy and reflection-type confocal microscopy to be used as detection methods. Voids could be arranged in a three-dimensional multilayered structure for high-density optical data storage. The separation of adjacent bits and layers were 4 and 16 μm, respectively.     

Optical Spectroscopy of Er^3＋ and Er^3＋/Yb^3＋ Co-doped Bi2O3-GeO2-B2O3-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＋ .     

Ultra-high sensitivity of rhodamine B sensing based on NaGdF4:Yb3+,Er3+@NaGdF4 core-shell upconversion nanoparticles

A series of mono-dispersed hexagon NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 core-shell nanoparticles with different shell thickness were synthesized via a co-precipitation method. Nanoparticles with high upconversion fluorescent emissions result in large signal-to-noise ratio, which guarantees the accuracy of the sensitivity. Besides, the maximum sensitivity of these NPs as detection film increases first and then decreases with the shell thickness increasing. When the shell thickness is 2.3 nm(NaGdF_4-2), the maximum sensitivity(0.69959 ppm~(-1)) is reached. A large degree of overlap between the rhodamine B absorption band and the Er~(3+) green emission bands ensures that the NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 nanoparticles can be used as fluorescent probe to detect the concentration of rhodamine B based on fluorescent intensity ratio technology. The linear relationship between the rhodamine B concentration and the intensity ratio(R) of green and red emission intensity(I_(S+H) and I_F) were studied systematically. The result shows that the maximum sensitivity can be obtained in low concentration rhodamine B(4 ppm), which is lower than the reported minimum detection concentration. Thus, the ultra-high sensitivity detection by NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 core-shell upconversion nanoparticles in low concentration can be realized,which provides promising applications in bio-detection filed.