Magneto-optic and luminescent properties of tellurite glass TeO<Subscript>2</Subscript>-ZnCl<Subscript>2</Subscript> doped with rare-earth elements

Tellurite glasses were synthesized on the basis of the binary system composed of 70 mol % TeO₂ and 30 mol % ZnCl₂ and doped with Nd³⁺, Pr³⁺, Tb³⁺, Er³⁺, Yb³⁺, Ho³⁺. The physicochemical, luminescent, and magneto-optic properties of these glasses were studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1262–1265.Original Russian Text Copyright © 2004 by Grishin, Gurev, Intyushin, Elliev, Pavlova, Savikin.     

Investigation on the upconversion luminescence of Sr3AlO4F:Yb3+, Er3+, Ho3+ phosphors

To develop new emission-tunable upconversion (UC) phosphors, the Sr₃AlO₄F:5%Yb³⁺, xEr³⁺, yHo³⁺ (0 ≤ x ≤ 1%, 0 ≤ y ≤ 1%) samples were prepared by conversional solid-state reaction method, and their luminescence properties upon 980 nm excitation were studied. Upon 980 nm excitation, Yb³⁺-Er³⁺ codoped Sr₃AlO₄F shows a predominant emission peak between 645 and 700 nm which is attributed to the ⁴F_9/2-⁴I_15/2 transition of Er³⁺, and the Er³⁺ green emissions have been almost quenched. In this case, the yellowish green emitting light is obtained. The possible reason was interpreted by the energy level diagram and the proposed UC mechanism. For Yb³⁺-Ho³⁺ codoped Sr₃AlO₄F, three emissions are observed obviously which are all derived from the Ho³⁺ ion. The corresponding chromaticity coordinates indicate a red emission has been gained. To realize the tunable emission, the typical Sr₃AlO₄F:5%Yb³⁺, 0.2%Er³⁺, 1%Ho³⁺ phosphor was developed, and its emission spectrum includes the emission peaks of both Er³⁺ and Ho³⁺. Correspondingly, the sample gives a yellow emission.     

Judd–Ofelt analysis and photoluminescence properties of RE3+ (RE = Er & Nd): Cadmium lithium boro tellurite glasses

Rare earth (Er³⁺ and Nd³⁺) ions doped cadmium lithium boro tellurite (CLiBT) glasses were prepared by melt quenching method. The vis–NIR absorption spectra of these glasses have been analyzed systematically. Judd–Ofelt intensity parameters Ω_λ (λ = 2, 4, 6) have been evaluated and used to compute the radiative properties of emission transitions of Er³⁺ and Nd³⁺: CLiBT glasses. From the NIR emission spectra of Er³⁺: CLiBT glasses a broad emission band centered at 1538 nm (⁴I_13/2 → ⁴I_15/2) is observed and from Nd³⁺: CLiBT glasses, three NIR emission bands at 898 nm (⁴F_3/2 → ⁴I_9/2), 1070 nm (⁴F_3/2 → ⁴I_11/2) and 1338 nm (⁴F_3/2 → ⁴I_13/2) are observed with an excitation wavelength λ_exci = 514.5 nm (Ar⁺ Laser). The FWHM and stimulated emission cross-section values are calculated for Er³⁺ and Nd³⁺: CLiBT glasses. FWHM × σ_e^P values are also calculated for Er³⁺: CLiBT glasses.     

DNA Intercalating Near-Infrared Luminescent Lanthanide Complexes Containing Dipyrido[3,2-a:2′,3′-c]phenazine (dppz) Ligands: Synthesis,Crystal Structures,Stability, Luminescence Properties and CT-DNA Interaction

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO₃)₃(dppz)₂] (Ln = Nd³⁺, Er³⁺ and Yb³⁺; dppz = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized, characterized and their luminescence properties were investigated. In addition, analogous compounds with other lanthanide ions (Ln = Ce³⁺, Pr³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Tm³⁺, Lu³⁺) were prepared. All complexes were characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction analysis of the complexes (Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Eu³⁺, Er³⁺, Yb³⁺, Lu³⁺) showed that the lanthanide’s first coordination sphere can be described as a bicapped dodecahedron, made up of two bidentate dppz ligands and three bidentate-coordinating nitrate anions. Efficient energy transfer was observed from the dppz ligand to the lanthanide ion (Nd³⁺, Er³⁺ and Yb³⁺), while relatively high luminescence lifetimes were detected for these complexes. In their excitation spectra, the maximum of the strong broad band is located at around 385 nm and this wavelength was further used for excitation of the chosen complexes. In their emission spectra, the following characteristic NIR emission peaks were observed: for a) Nd³⁺: ⁴F_3/2 → ⁴I_9/2 (870.8 nm), ⁴F_3/2 → ⁴I_11/2 (1052.7 nm) and ⁴F_3/2 → ⁴I_13/2 (1334.5 nm); b) Er³⁺: ⁴I_13/2 → ⁴I_15/2 (1529.0 nm) c) Yb³⁺: ²F_5/2 → ²F_7/2 (977.6 nm). While its low triplet energy level is ideally suited for efficient sensitization of Nd³⁺ and Er³⁺, the dppz ligand is considered not favorable as a sensitizer for most of the visible emitting lanthanide ions, due to its low-lying triplet level, which is too low for the accepting levels of most visible emitting lanthanides. Furthermore, the DNA intercalation ability of the [Nd(NO₃)₃(dppz)₂] complex with calf thymus DNA (CT-DNA) was confirmed using fluorescence spectroscopy.     

Compositional effects and spectroscopy of rare earths (Er, Tm, and Nd) in tellurite glasses

Tellurium oxide glass hosts have exceptionally large solubility for RE-ions. In this paper, the relationship between the host glass composition and spectroscopic properties of Er³⁺-doped and Tm³⁺-doped tellurite glasses and fibres has been examined in detail. In particular, the effect of compositional modification on the line-shapes of the transitions: ⁴I_13/2→⁴I_15/2 in Er³⁺-doped and ³H₄→³F₄ in Tm³⁺-doped tellurite glasses is analysed and discussed. The presence of co-dopants, namely Tb³⁺ and Ho³⁺ ions in Tm³⁺-doped glasses on the lifetimes of the upper (³H₄) and the lower (³F₄) levels have also been discussed for shortening the lifetime of the transition between the ³F₄ level and the ground state in thulium. The spectroscopic properties of Nd³⁺-doped glasses for designing amplifiers operating in the 1330- to 1370-nm region has also been explained for demonstrating a continuous gain spectrum from 1310- to 1610-nm. The fibre loss measurements demonstrate that the Er-doped fibres have less than 880 dB km^–1 attenuation in the 1200- to 1400-nm range. An explanation is given to determine the suitability of such RE-doped tellurite fibres for designing broadband amplifiers.     

Structural and Spectroscopic Effects of Li+ Substitution for Na+ in LixNa1-xCaGd0.5Ho0.05Yb0.45(MoO4)3 Scheelite-Type Upconversion Phosphors

A set of new triple molybdates, Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45, was successfully manufactured by the microwave-accompanied sol–gel-based process (MAS). Yellow molybdate phosphors Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45 with variation of the Li_xNa_1-x (x = 0, 0.05, 0.1, 0.2, 0.3) ratio under constant doping amounts of Ho³⁺ = 0.05 and Yb³⁺ = 0.45 were obtained, and the effect of Li⁺ on their spectroscopic features was investigated. The crystal structures of Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) at room temperature were determined in space group I4₁/a by Rietveld analysis. Pure NaCaGd_0.5Ho_0.05Yb_0.45(MoO₄)₃ has a scheelite-type structure with cell parameters a = 5.2077 (2) and c = 11.3657 (5) Å, V = 308.24 (3) ų, Z = 4. In Li-doped samples, big cation sites are occupied by a mixture of (Li,Na,Gd,Ho,Yb) ions, and this provides a linear cell volume decrease with increasing Li doping level. The evaluated upconversion (UC) behavior and Raman spectroscopic results of the phosphors are discussed in detail. Under excitation at 980 nm, the phosphors provide yellow color emission based on the ⁵S₂/⁵F₄ → ⁵I₈ green emission and the ⁵F₅ → ⁵I₈ red emission. The incorporated Li⁺ ions gave rise to local symmetry distortion (LSD) around the cations in the substituted crystalline structure by the Ho³⁺ and Yb³⁺ ions, and they further affected the UC transition probabilities in triple molybdates Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45. The complex UC intensity dependence on the Li content is explained by the specificity of unit cell distortion in a disordered large ion system within the scheelite crystal structure. The Raman spectra of Li_xNa_1-xCaGd_0.5(MoO₄)₃ doped with Ho³⁺ and Yb³⁺ ions were totally superimposed with the luminescence signal of Ho³⁺ ions in the range of Mo–O stretching vibrations, and increasing the Li⁺ content resulted in a change in the Ho³⁺ multiplet intensity. The individual chromaticity points (ICP) for the LiNaCaGd(MoO₄)₃:Ho³⁺,Yb³⁺ phosphors correspond to the equal-energy point in the standard CIE (Commission Internationale de L’Eclairage) coordinates.     

Frequency upconversion in rare-earth doped fluoroindate glasses

We present recent results on frequency upconversion (UPC) obtained in fluoroindate glasses (FIG) doped with Ho³⁺, Tm³⁺ and Nd³⁺ ions and codoped with Pr³⁺/Nd³⁺ and Yb³⁺/Tb³⁺ ions. The results for the Ho³⁺-doped samples show strong evidence of energy transfer (ET) between Ho³⁺ ions resonantly excited at 640 nm. The origin of the blue-green upconverted fluorescence observed was identified and the dynamics of the signals revealed the pathways involved in the UPC process. In the case of Tm³⁺-doped FIG, the samples were resonantly excited at 650 nm and the main mechanism that contributes for the red-to-blue upconversion is excited-state absorption (ESA). The FIG samples codoped with Pr³⁺/Nd³⁺ were excited at 588 nm in resonance with transitions starting from the ground state of the Nd³⁺ and the Pr³⁺ ions. It was observed that the presence of Nd³⁺ ions enhanced the Pr³⁺ emission at 480 nm by two orders of magnitude. Multiphonon (MP)-assisted upconversion is also discussed for Nd³⁺-doped FIG pumped at 866 nm. Emission at 750 nm with a peculiar linear dependence with the laser intensity was observed and explained. A rate-equation model that includes MP absorption via thermally coupled electronic excited states of Nd³⁺ was developed and describes well the experimental results. The role played by effective phonon modes is clearly demonstrated. MP-assisted UPC process was also studied in Yb³⁺/Tb³⁺-codoped FIG samples excited at 1064 nm, which is off-resonance with electronic transitions starting from the ground state. It was determined that the mechanism leading to Tb³⁺ emission in the blue is due to ET from a pair of excited Yb³⁺ ions followed by ESA in the Tb³⁺ ions.     

The crystal and magnetic structures of Ca2NdRuO6, Ca2HoRuO6, and Sr2ErRuO6

The crystal structure of Sr₂ErRuO₆ has been refined from neutron powder diffraction data collected at room temperature; space group P2₁/n, A = 5.7626(2), B = 5.7681(2), C = 8.1489(2) Å, β = 90.19(1)°. The structure is that of a distorted perovskite with a 1:1 ordered arrangement of Ru⁵⁺ and Er³⁺ over the 6-coordinate sites. Data collected at 4.2 K show the presence of long range antiferromagnetic order involving both Ru⁵⁺ and Er³⁺. The temperature dependence of the sublattice magnetizations is described. The crystal structure of Ca₂NdRuO₆ is also that of a distored perovskite (P2₁/n, A = 5.5564(1), B = 5.8296(1), C = 8.0085(1) β = 90.19(1)°. The β = 90.07(1)°) with a random distribution of Ca²⁺ and Nd³⁺ on the A site and a 1:1 ordered arrangement of Ca²⁺ and Ru⁵⁺ on the 6-coordinate B sites. The Ru⁵⁺ sublattice is antiferromagnetic at 4.2 K but there is no evidence for magnetic ordering of the Nd³⁺ ions. Ca₂HoRuO₆ is also a distorted perovskite (P2₁/n, A = 5.4991(1), B = 5.7725(1), C = 7.9381(2), β = 90.18(1)° at 4.2 K) with a cation distribution best represented as Ca_1.46Ho_0.54[Ca_0.54Ho_0.46Ru]O₆. There is no ordering among the Ca³⁺ or Ho³⁺ ions on either the A or the B sites, but the Ca/Ho ions form a 1:1 ordered arrangement with Ru⁵⁺ on the B sites. At 4.2 K the Ru⁵⁺ ions adopt a Type I antiferromagnetic arrangement but there is no evidence of long range magnetic ordering among the Ho³⁺ ions.     

Sol–gel preparation and white up-conversion luminescence in rare-earth doped PbF<Subscript>2</Subscript> nanocrystals dissolved in silica glass

89.5(SiO₂)10(PbF₂)0.5(REF₃) silicate glasses have been prepared using room temperature sol–gel processing of Si(OCH₂CH₃)₄, Pb(CH₃COO)₂·3H₂O, RE(CH₃COO)₃·nH₂O and trifluoroacetic acid as a fluorinating agent, where RE stands for rare-earth ions, such as Yb³⁺, Er³⁺, Ho³⁺, Tm³⁺, or combinations of those ions. On heat treatment of these glasses at about 300–400 °C, the rare-earth doped spherical PbF₂ nanocrystals precipitate within SiO₂ glass matrix providing transparent nano-structured glass–ceramics, while the diameter of the nanocrystals can be set in the range from 5 to 25 nm by varying time and temperature of the heat treatment. The structural and photoluminescence studies confirm the incorporation of rare-earth ions into the PbF₂ nanocrystals and white and tuneable colour up-conversion luminescence has been detected in case of Yb³⁺-Er³⁺-Tm³⁺ and Yb³⁺-Ho³⁺-Tm³⁺ co-doped nanocrystals by varying dopant ratio and pump power.     

Preparation and up-conversion fluorescence of rare earth (Er or Yb/Er)-doped TiO2 nanobelts

Anatase TiO₂ nanobelts doped with rare earth (RE) ions Yb³⁺, Er³⁺ or Yb³⁺/Er³⁺ have been prepared using layered titanate nanobelts (LTO NBs) with RE ions as the precursor obtained by ion-exchange between LTO NBs and RE ions under hydrothermal process. Various measurement results demonstrate that the RE ions have doped into the lattice of TiO₂, and the Er³⁺ or Yb³⁺/Er³⁺ doped nanobelts show strong visible up-conversion (UC) fluorescence under 980 nm excitation. The UC emission intensity of LTO NBs embedded with Er³⁺ or Yb³⁺/Er³⁺ is slightly higher than that of the corresponding TiO₂ nanobelts doped with RE ions, whereas higher RE doping content leads to the decrease of UC emission intensity due to the concentration-quenching effect.     

Rare-earth-doped glasses for fiber amplifiers in broadband telecommunication

Rare-earth-doped optical amplifiers have a great potential for broadband Wavelength-Division-Multiplexed (WDM) telecommunication by tailoring host glass compositions. In order to design the emission spectra of doped rare-earth ions, it is important to understand the relationship between the local ligand field and various optical properties of specific 4f-levels, such as the radiative transition probability, the nonradiative decay probability, which dominate the spectral line width and quantum efficiency of amplification transitions. For the Er³⁺:1.55 μm transition, the role of the Judd–Ofelt Ω₆ parameters is presented, which is correlated to the Er–ligand bond covalency in glasses. The Tm³⁺: 1.46-μm transition shows quantum efficiency over 90% high enough for the S-band application, in heavy metal oxide glasses with moderate phonon energy and wider spectra than fluorides. A way to improve population inversion by selective energy transfer with codoped lanthanide ions is presented. Finally, the energy level structures and resultant spectral properties of Pr³⁺, Nd³⁺ and Dy³⁺ ions, 1.3-μm-active ions, are compared. The hypersensitivity of Dy³⁺ transitions appears especially in chalcogenide glasses, where the nonradiative loss due to multiphonon decay is also minimized. In conclusion, glass materials have opportunities to vary the radiative cross section, quantum efficiency, and gain flatness, which are important for novel amplifiers in the future DWDM system.     

Optical transitions of Mn2+ in fluoride glasses

The optical properties of Mn²⁺ ions have been extensively investigated in numerous host materials. The 3d⁵ electrons associated with the manganese ion are sensitive to crystal field and the optical transitions yield valuable information on the local environment. Thus, the Mn²⁺ ion optical spectra in fluorozirconate and fluorohafnate glasses suggest that these ions are in positions of low crystal field. Most likely Mn²⁺ substitutes for Ba²⁺ ions in these glasses. As the glass undergoes devitrification the Mn²⁺ ion spectrum changes suggesting that optical methods can be used for studying the temperature dependence of glass transitions.     

Photoacoustic spectroscopic studies of Ho3+, Er3+, and Sm3+ doped polyvinyl alcohol films

Photoacoustic (PA) spectra of Ho³⁺, Er³⁺, and Sm³⁺ doped PVA films were obtained in 350–800 nm range. PA spectra were also obtained for the respective dopant oxides: Ho₂O₃, Er₂O₃, and Sm₂O₃ for comparison. It was found that in PVA the PA sensitivity has increased considerably compared to pure rare earth oxides. The relative intensities of absorption bands at 540 and 637 nm of Ho₃₊: PVA have shown distinct enhancement, indicating the increase in nonradiative relaxation at these excitations. Furthermore, the PA signals at wavelengths for different PA absorption bands were monitored as a function of chopping frequency. These experiments have shown that PA signal varies w⁻¹ both for oxides and PVA samples, suggesting that they behave as thermally thin samples. © 1997 John Wiley & Sons, Inc.     

Structural and luminescent study in lanthanide doped sol–gel glass–ceramics comprising CeF<Subscript>3</Subscript> nanocrystals

Sol–gel derived glass–ceramics containing CeF₃ nanocrystals have been developed for the first time, to the best of our knowledge, by adequate heat treatments of precursor bulk glasses with composition 95SiO₂–5CeF₃ doped with 0.1 Eu³⁺ or 0.1 Sm³⁺ and co-doped with 0.3 Yb³⁺ and 0.1 Er³⁺ ions (in mol%). X-Ray Diffraction and High Resolution Transmission Electron Microscopy confirm the precipitation of CeF₃ nanocrystals. Moreover, this structural analysis is completed using Eu³⁺ and Sm³⁺ as probe ions of the different local environments for rare-earth ions in the nano-structured glass–ceramics. Luminescence measurements led us to discern the final environments for the ions, revealing the partition of a large fraction of these ions into like-crystalline environment of the precipitated CeF₃ nanocrystals. Near infrared emission at 1.5 μm was observed after excitation at 980 nm in Yb³⁺–Er³⁺ co-doped samples for potential applications in telecommunications.     

Lanthanide-doped LiYF4 nanoparticles: Synthesis and multicolor upconversion tuning

We report the synthesis of tetragonal-phase LiYF₄ nanoparticles doped with upconverting lanthanide ions. The nanoparticles have been characterized by XRD, TEM, and luminescence decay studies. The size of the as-synthesized LiYF₄ nanoparticles can be tuned by varying the precursor ratio of F to lanthanide ions. Passivated by oleic acid ligands, the LiYF₄ nanoparticles can be readily dispersed in a wide range of nonpolar solvents including hexane, cyclohexane, dichloromethane, and toluene. The lanthanide-doped (Yb³⁺, Er³⁺, Tm³⁺, Ho³⁺) LiYF₄ nanoparticles show intense upconversion emissions upon near infrared excitation at 980 nm. By varying composition and concentration of the dopant ions, the color output can be precisely modulated under single wavelength excitation with a diode laser.     

Bi3+‐Er3+ and Bi3+‐Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near‐Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f‐electron emission at 1540 nm (suitable for low‐loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺‐Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature‐dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

Compositional effects and spectroscopy of rare earths (Er3+, Tm3+, and Nd3+) in tellurite glasses

Tellurium oxide glass hosts have exceptionally large solubility for RE-ions. In this paper, the relationship between the host glass composition and spectroscopic properties of Er³⁺-doped and Tm³⁺-doped tellurite glasses and fibres has been examined in detail. In particular, the effect of compositional modification on the line-shapes of the transitions: ⁴I_13/2→⁴I_15/2 in Er³⁺-doped and ³H₄→³F₄ in Tm³⁺-doped tellurite glasses is analysed and discussed. The presence of co-dopants, namely Tb³⁺ and Ho³⁺ ions in Tm³⁺-doped glasses on the lifetimes of the upper (³H₄) and the lower (³F₄) levels have also been discussed for shortening the lifetime of the transition between the ³F₄ level and the ground state in thulium. The spectroscopic properties of Nd³⁺-doped glasses for designing amplifiers operating in the 1330- to 1370-nm region has also been explained for demonstrating a continuous gain spectrum from 1310- to 1610-nm. The fibre loss measurements demonstrate that the Er-doped fibres have less than 880 dB km^–1 attenuation in the 1200- to 1400-nm range. An explanation is given to determine the suitability of such RE-doped tellurite fibres for designing broadband amplifiers.     

Comparative investigation on structure and luminescence properties of fluoride phosphors codoped with Er/Yb

This paper reports on comparative investigation of structure and luminescence properties of tetragonal LiYF₄ and BaYF₅, and hexagonal NaYF₄ phosphors codoped with Er³⁺/Yb³⁺ by a facile hydrothermal synthesis. The products were characterized by X-ray diffractometer, scanning electron microscope, and photoluminescence spectroscopy. Intense visible emissions centered at around 525, 550 and 650 nm, originated from the transitions of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 of Er³⁺, respectively, have been observed in all the samples upon excitation with a 980 nm laser diode, and the involved mechanisms have been explained. Based on the green up-conversion emission performance, the Yb³⁺ concentrations of Er³⁺/Yb³⁺-codoped LiYF₄, BaYF₅, and NaYF₄ phosphors have been optimized to be 10, 20, and 20 mol.%, respectively. The quadratic dependence of fluorescence on excitation laser power has confirmed that two-photon contribute to up-conversion of the green–red emissions.     

Fluorescence of rare earth ions adsorbed on porous vycor glass

Fluorescence of rare earth (RE) ions arising from f—f transitions in Pr³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺ and Tm³⁺ was observed front the ions adsorbed on porous Vycor glass or on pressed discs of fumed silica. The non-radiative relaxations of the excited states were depressed as a result of a strong chemical bond between the ions and silica acting as a ligand.     

Vacuum ultraviolet and near-infrared excited luminescence properties of Ca3(PO4)2:RE, Na (RE=Tb, Yb, Er, Tm, and Ho)

Tb³⁺, Yb³⁺, Tm³⁺, Er³⁺, and Ho³⁺ doped Ca₃(PO₄)₂ were synthesized by solid-state reaction, and their luminescence properties were studied by spectra techniques. Tb³⁺-doped samples can exhibit intense green emission under VUV excitation, and the brightness for the optimal Tb³⁺ content is comparable with that of the commercial Zn₂SiO₄:Mn²⁺ green phosphor. Under near-infrared laser excitation, the upconversion luminescence spectra of Yb³⁺, Tm³⁺, Er³⁺, and Ho³⁺ doped samples demonstrate that the red, green, and blue tricolored fluorescence could be obtained by codoping Yb³⁺-Ho³⁺, Yb³⁺-Er³⁺, and Yb³⁺-Tm³⁺ in Ca₃(PO₄)₂, respectively. Good white upconversion emission with CIE chromaticity coordinates (0.358, 0.362) is achieved by quadri-doping Yb³⁺-Tm³⁺-Er³⁺-Ho³⁺ in Ca₃(PO₄)₂, in which the cross-relaxation process between Er³⁺ and Tm³⁺, producing the ¹D₂-³F₄ transition of Tm³⁺, is found. The upconversion mechanisms are elucidated through the laser power dependence of the upconverted emissions and the energy level diagrams.