Intense Upconversion Luminescence of CaSc2O4:Ho3+/Yb3+ from Large Absorption Cross Section and Energy‐Transfer Rate of Yb3+

Concentration‐optimized CaSc₂O₄:0.2 % Ho³⁺/10 % Yb³⁺ shows stronger upconversion luminescence (UCL) than a typical concentration‐optimized upconverting phosphor Y₂O₃:0.2 % Ho³⁺/10 % Yb³⁺ upon excitation with a 980 nm laser diode pump. The ⁵F₄+⁵S₂→⁵I₈ green UCL around 545 nm and ⁵F₅→⁵I₈ red UCL around 660 nm of Ho³⁺ are enhanced by factors of 2.6 and 1.6, respectively. On analyzing the emission spectra and decay curves of Yb³⁺: ²F_5/2→²F_7/2 and Ho³⁺: ⁵I₆→⁵I₈, respectively, in the two hosts, we reveal that Yb³⁺ in CaSc₂O₄ exhibits a larger absorption cross section at 980 nm and subsequent larger Yb³⁺: ²F_5/2→Ho³⁺: ⁵I₆ energy‐transfer coefficient (8.55×10^?17 cm³ s^?1) compared to that (4.63×10^?17 cm³ s^?1) in Y₂O₃, indicating that CaSc₂O₄:Ho³⁺/Yb³⁺ is an excellent oxide upconverting material for achieving intense UCL.     

Hydrothermal Synthesis and Up‐conversion Luminescence of Ho3+/Yb3+ Co‐doped PbTiO3

Ho³⁺/Yb³⁺ co‐doped PbTiO₃ nanocrystals with different content of dopant were successfully prepared via a facile hydrothermal method. The purity, morphology, element distribution, chemical state and up‐conversion (UC) photoluminescence (PL) of PbTiO₃ nanocrystals affected by Ho³⁺ dopant are investigated systematically. X‐ray diffraction (XRD) results illustrate that PbTiO₃ samples with the doping Ho³⁺ concentration ranging from 0 to 5 mol‐% are perovskite structure. The doping Ho³⁺ ions have no change on the crystal structure of perovskite PbTiO₃. Owing to the non‐equivalent substitution of Ho³⁺ to Ti⁴⁺ in PbTiO₃, the particle size of Ho³⁺/Yb³⁺ co‐doped PbTiO₃ samples is decreased as well as the particle agglomeration is detected. Moreover, Ho and Yb ions have uniform distributions in the PbTiO₃ nanoparticles as the presence of Ho³⁺ and Yb³⁺ cations. The up‐conversion spectra demonstrate that Ho/Yb co‐doped PbTiO₃ samples have up‐conversion emissions centered at 550 nm, 660 nm and 755 nm, corresponding to the transitions of ⁵F₄(⁵S₂)→⁵I₈, ⁵F₅→⁵I₈ and ⁵S₂(⁵F₄)→⁵I₇ of Ho³⁺ ions. Additionally, the effect of temperature on the UC PL property of Ho³⁺/Yb³⁺ co‐doped PbTiO₃ system is further investigated. The sensitivity and the trend of Ho³⁺/Yb³⁺ co‐doped PbTiO₃ samples in temperature from 298 k to 493K are calculated on the basis of fluorescence intensity ratio (FIR) method. Ho³⁺/Yb³⁺ co‐doped PbTiO₃ nanocrystals are verified the high potential in the optical temperature sensing.     

Luminescence Tuning of Upconversion Nanocrystals

Upconversion luminescence tuning of β‐NaYF₄ nanorods under 980 nm excitation has successfully been achieved by tridoping with Ln³⁺ ions with different electronic structures. The effects of Ce³⁺ ions on NaYF₄:Yb³⁺/Ho³⁺ as well as Gd³⁺ ions on NaYF₄:Yb³⁺/Tm³⁺(Er³⁺) have been studied in detail. By tridoping with Ce³⁺ ions, not only were unusual ⁵G₅→⁵I₇ and ⁵F₂/³K₈→⁵I₈ transitions from Ho³⁺ ions and 5d→4f transitions from Ce³⁺ ions observed in NaYF₄:Yb³⁺/Ho³⁺ nanorods, but also an increase in the intensity of ⁵F₅→⁵I₈ relative to ⁵S₂/⁵F₄→⁵I₈ with increasing Ce³⁺ concentration, which can be attributed to efficient energy transfers of ⁵I₆ (Ho)+²F_5/2 (Ce)→⁵I₇ (Ho)+²F_7/2 (Ce) and ⁵S₂/⁵F₄ (Ho)+²F_5/2 (Ce)→⁵F₅ (Ho)+²F_7/2 (Ce). Interestingly, with increasing pump power density, the luminescence of NaYF₄:Yb³⁺/Ho³⁺ nanorods is always dominated by the ⁵S₂/⁵F₄→⁵I₈ transition, whereas the luminescence of Ce³⁺‐tridoped NaYF₄:Yb³⁺/Ho³⁺ nanorods is dominated by the ⁵S₂/⁵F₄→⁵I₈ and ⁵G₅→⁵I₇ transitions in turn. These observations are discussed on the basis of a rate equation model. Furthermore, Gd³⁺‐tridoped NaYF₄:Yb³⁺/Tm³⁺(Er³⁺) nanorods can emit multicolor upconversion emissions spanning from the UV to the near‐infrared under 980 nm excitation. ⁶P_5/2→⁸S_7/2 (≈306 nm) and ⁶P_7/2→⁸S_7/2 (≈311 nm) transitions from Gd³⁺ ions were observed. In addition to the aforementioned luminescence properties, these Gd³⁺‐tridoped nanorods also exhibit paramagnetic behavior at room temperature and superparamagnetic behavior at 2 or 5 K.     

Upconversion Luminescence Properties of a LiNb0.3Ta0.7O3:Er3+,Yb3+ Ceramic

A co-doped LiNb_0.3Ta_0.7O₃:Er³⁺,Yb³⁺ ceramic was prepared by a high temperature solid state procedure. Under the excitation of 980 nm laser radiation, intense 660 nm red light and 550 nm green light emissions corresponding to the ⁴F_9/2→⁴I_15/2 and ²H_11/2/⁴S_3/2→⁴I_15/2 transitions of Er³⁺ were observed. The change of Yb³⁺ concentration has a more significant influence on luminous intensity than the Er³⁺ concentration. The emission of red and green lights is attributed to a two-photon process. The upconversion luminescence mechanisms were analyzed in detail.     

Infrared‐to‐Visible Light Conversion in Er3+–Yb3+:Lu3Ga5O12 Nanogarnets

Er³⁺–Yb³⁺ co‐doped Lu₃Ga₅O₁₂ nanogarnets were prepared and characterized; their structural and luminescence properties were determined as a function of the Yb³⁺ concentration. The morphology of the nanogarnets was studied by HRTEM. Under 488 nm excitation, the nanogarnets emit green, red, and near‐infrared light. The decay curves for the (⁴S_3/2, ²H_11/2) and ⁴F_9/2 levels of the Er³⁺ions exhibit a non‐exponential nature under resonant laser excitation and their effective lifetimes are found to decrease with an increase in the Yb³⁺ concentration from 1.0 to 10.0 mol %. The non‐exponential decay curves are well fitted to the Inokuti–Hirayama model for S=8, indicating that the mechanism of interaction for energy transfer between the optically active ions is of dipole–quadrupole type. Upon 976 nm laser excitation, an intense green upconverted emission is clearly observed by the naked eyes. A significant enhancement of the red‐to‐green intensity ratio of Er³⁺ ions was observed with an increase in Yb³⁺ concentration. The power dependence and the dynamics of the upconverted emission confirm the existence of two‐photon upconversion processes for the green and red emissions.     

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.     

Intensity parameters,radiative transitions and non-radiative relaxations of Ho3+ in various tellurite glasses

The intensity parameters of holmium in sodium, barium and zinc tellurite glasses were obtained from the absorption spectra. Using these parameters and the matrix elements of Ho³⁺, transition probabilities and branching ratios from the excited states (⁵F₄, ⁵S₂), ⁵F₅, ⁵I₄, ⁵I₅ and ⁵I₆ were calculated. Quantum efficiencies for the (⁵F₄, ⁵S₂) state were obtained and the multiphonon transition rates calculated at room temperature. Non-radiative multiphonon relaxations were obtained from the (⁵F₄, ⁵S₂) level. The relaxation increased in the order of zinc, barium, sodium, and is assumed to be dependent on the local site symmetry of Ho³⁺ in glass.     

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.     

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.     

Visible Up-Conversion Luminescence in Ho3+: BaTiO3 Nano-Crystals Prepared by Sol Gel Technique

Visible up-conversion emissions at (435, 545, 580, 675 and 690 nm) and (437, 547 575 and 675 nm) have been observed from the sol-gel derived nano-crystalline Ho³⁺: BaTiO₃ powders and thin films respectively, under 808 nm laser diode excitation emissions. Combined with the energy level structure of Ho³⁺ ions and the kinetics of the visible emissions, the up-conversion mechanism has been analyzed and explained. The blue, green and red emissions of both samples has been attributed to the ground state-directed transition from (⁵F₁), (⁵S₂) and (⁵F₅), which are populated through excited state absorption (ESA) for 808 nm excitation. Nano-structure pure barium titanate and doped with different concentrations of Ho³⁺ ions in the from of powder and thin film have been prepared by sol-gel technique, using barium acetate (Ba(Ac)₂), and titanium butoxide (Ti(C₄H₉O)₄), as precursors. The thin films were prepared by sol-gel spin coating method. The as-grown thin films and powders were found to be amorphous, which crystallized to the tetragonal phase after heating at 750°C in air for 30 minutes. The crystallite sizes of the thin film and powder both doped with 4% Ho³⁺ ions was found to be equal to 11 and 16 nm, respectvely.     

Up-converted luminescence in Yb,Tm co-doped LaGaO3 phosphors by high-energy ball milling and solid state reaction

LaGaO₃:Tm³⁺, Yb³⁺ powder was synthesized by a high-energy ball milling (HEB) and a conventional solid state reaction (SSR). The X-ray diffraction patterns confirmed the LaGaO₃:Tm³⁺, Yb³⁺ powder phosphors to have an orthorhombic structure. The spectrum consisted of ¹G₄ → ³H₆, weak ¹G₄ → ³F₄, and intense ³H₄ → ³H₆ transition bands within the f¹² configuration of Tm³⁺, together with the ²F_5/2 → ²F_7/2 transition of Yb³⁺. Up-converted emission of the LaGaO₃:Tm³⁺, Yb³⁺ powders were observed under laser diode excitation of 975 nm. The PL intensity of the HEB-LaGaO₃:Tm³⁺, Yb³⁺ powders sintered at 1300 °C were higher than those of all LaGaO₃:Tm³⁺, Yb³⁺ powder samples examined. The energy transition probability of HEB-LaGaO₃:Tm³⁺, Yb³⁺ powders are higher than that of the SSR-LaGaO₃:Tm³⁺, Yb³⁺ powders. Compared to the solid state reaction method, synthesis by high-energy ball milling is simple and provides improved crystallinity of the host.     

Unique Spectral Overlap and Resonant Energy Transfer between Europium(II) and Ytterbium(III) Cations: No Quantum Cutting

Samples of the Ca₃Sc₂Si₃O₁₂ (CSS) host singly doped with Eu²⁺ or Yb³⁺, doubly doped with Eu²⁺ and Yb³⁺, and triply doped with Ce³⁺, Eu²⁺ and Yb³⁺ were synthesized by a sol–gel combustion process under reducing conditions. Unlike previous reports of Eu²⁺→Yb³⁺ energy transfer in other systems, the energy transfer is resonant in the CSS host and the transfer efficiency reaches 100 % for lightly doped samples. The transfer mechanism is multipolar rather than electron transfer for the sample compositions employed herein. The emission intensity of Yb³⁺ is further enhanced by co‐doping with Ce³⁺ in addition to Eu²⁺. The quantum efficiencies of the doped materials range between 9 % and 93 %.     

Ho3+/Yb3+共掺ZnO-Al2O3-GeO2-SiO2玻璃陶瓷的制备和上转换发光性质

综合ZnO-Al₂O₃-SiO₂系和锗酸盐玻璃陶瓷的优点,采用熔融-晶化法首次制备了Ho³⁺/Yb³⁺共掺以ZnAl₂O₄为主晶相的ZnO-Al₂O₃-GeO₂-SiO₂系玻璃陶瓷。因[GeO₄]四面体和[SiO₄]四面体都是玻璃网络形成体,讨论了GeO₂取代SiO₂对玻璃陶瓷样品硬度及发光性能的影响,最终确定GeO₂的取代量为10.55%（w/w）时,玻璃陶瓷综合性能最佳。在980 nm泵浦光的激发下,发现强的绿色（546 nm）和弱的红色（650 nm）上转换发光,并研究了不同Ho³⁺/Yb³⁺掺杂比对样品上转换发光的影响,最终结果表明当Ho³⁺/Yb³⁺掺杂比为1：11（n/n）时样品荧光强度最强,在绿色上转换发光材料方面具有潜在的应用。     

Spectral migration of excitation energy among Nd3+ ions in fluoroarsenate glasses

In this work, we have investigated the existence of energy transfer among Nd³⁺ ions in fluoroarsenate glasses of the Na₄As₂O₇, BaF₂, YF₃ system with different Nd³⁺ concentrations (0.5, 2, 3, 4, and 5 mol%) by using time-resolved fluorescence line narrowing spectroscopy. The spectral features of the time resolved fluorescence line narrowing ⁴F_3/2→⁴I_9/2 emission spectra obtained under resonant excitation reveal the existence of spectral migration of excitation among the Nd³⁺ ions. The analysis of the time evolution of the ⁴F_3/2→⁴I_9/2 narrowed emission shows that the electronic mechanism responsible for the ion–ion interaction can be identified as a dipole–dipole energy transfer process.     

Upconversion Luminescence from Ho3+ and Yb3+ Codoped α-NaYF4 Single Crystals

The Ho³⁺/Yb³⁺ co-doped α-NaYF₄ single crystal was grown successfully for the first time by a modified Bridgman method in which KF was used as assisting flux and a large temperature gradient (70-90 oC/cm) of solid-liquid interface was adopted. Upconversion emissions at green ～544 nm, red ～657 and ～751 nm were obtained under 980 nm laser diode excitation. The intensity at ～544 nm was much stronger than those of ～657 and ～751 nm. The mechanisms of the upconversion emissions were investigated by studying the relationship between the upconversion intensity and pump power. The optimized Yb³⁺ concentration was about 8.08 mol% when Ho³⁺ concentration was hold at about 1.0 mol%. The results showed that Ho³⁺/Yb³⁺+ doped α-NaYF₄ single crystal was a possible candidate upconversion material for the green solid-state laser.     

A general approach for selective enhancement of green upconversion emissions in Er3+ doped oxides by Yb3+–MoO4 2− dimer sensitizing

In this paper, we report a general approach to enhance the upconversion (UC) luminescence of Er³⁺ doped oxides phosphors by Yb³⁺–MoO₄ ^2? dimer sensitizing, which induced strong green UC emissions under the 976 nm laser diode excitation. By codoping of Yb³⁺ and Mo⁶⁺ in the Er³⁺ doped TiO₂ and ZnO, the green UC emissions intensity can be selectively increased about 10 and 500 times than those of Er³⁺–Yb³⁺ codoped TiO₂ and ZnO, respectively. The high excited state energy transfer between |²F_7/2, ³T₂> state of Yb³⁺–MoO₄ ^2? dimer and ⁴F_7/2 level of Er³⁺ significantly avoids the nonradiative decay processes happened at lower energy levels of Er³⁺, and then increases the green UC emissions efficiently. The proposed Yb³⁺–MoO₄ ^2? dimer sensitizing has been realized as an efficient way to enhance the green UC emissions in other Er³⁺ doped oxides phosphors. It is expected that the selective enhanced green UC emissions sensitized by Yb³⁺–MoO₄ ^2? dimer in Er³⁺ doped oxides phosphors can greatly extend their scope of applications.     

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.     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.     

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.     

Enhanced upconversion emission in Er3+-doped tellurite glass containing silver nanoparticles

Er³⁺-doped tellurite glass containing silver nanoparticles (NPs) has been synthesized. Detailed structural and optical characterizations have been carried out. Infrared to visible frequency upconversion (UC) emission has been observed in Er³⁺-doped tellurite glass on pumping with the 976 nm radiation. Further, an enhancement in UC emission intensity of green bands (²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2) of Er³⁺ ion has been observed up to four times in presence of silver NPs in the glass annealed at 240 °C for 40 h. Though, there is enhancement in intensity in the red band (⁴F_9/2 → ⁴I_15/2) also but it is smaller. The enhancement in fluorescence intensity is attributed to local field effect due to the silver NPs.