New multinuclear europium(III) complexes as phosphors applied in fabrication of near UV-based light-emitting diodes

Two new multinuclear europium(III) complexes, [Eu(AFTFBD)₃]₂(1,4-bmb) and [Eu(AFTFBD)₃]₃(tmb) were designed and synthesized, where HAFTFBD was 2-acetylfluorene-4,4,4-trifluorobutane-1,3-dione, 1,4-bmb was 1,4-bis[2-(2′-pyridyl)benzimidazolyl]benzene and tmb was 1,3,5-tris[2-(2′-pyridyl)benzimidazolyl]benzene. The complexes were characterized by IR, UV–visible, photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). The complexes emit the characteristic red luminescence of Eu³⁺ ion due to the ⁵D₀–⁷F_J (J = 0–4) transitions under 395 nm-light excitation. Bright red light-emitting diodes were fabricated by coating the selected complex (Eu(AFTFBD)₃)₃(tmb) onto ～395 nm-emitting InGaN chips, and the LEDs show appropriate CIE chromaticity coordinates in red area. All these results suggest that the Eu(III) complexes are promising candidates as red component for application in fabrication of near UV-based white light-emitting diodes.     

Structure and magnetism of novel dinuclear cobalt(II) complexes

Two dinuclear cobalt(II) complexes of the formula [Co₂X₄(isonia)₄] have been synthesized and structurally characterized; isonia is unidentate neutral iso-nicotinamide and X are furan-3- or furan-2-carboxylate ligands. The chromophore {CoO₄N₂} is formed of two iso-nicotinamide ligands and three furancarboxylate ligands where two of them bear a bridging function and one is a terminal-bidentate ligand. The magnetic data confirm a weak exchange interaction (J / hc = − 2 cm^− 1) and a high single-ion zero-field splitting (D / hc = 63 and 33 cm^− 1, respectively).     

A luminescent quadruple stranded dinuclear Eu(III) complex based on 2,8-bis(4′,4′,4′-trifluoro-1′,3′-dioxobutyl)-dibenzothiophene for light-emitting diodes

A luminescent quadruple stranded dinuclear Eu(III) complex Na₂[Eu₂(dbt)₄] was synthesized, where H₂dbt was 2,8-bis(4′,4′,4′-trifluoro-1′,3′-dioxobutyl)-dibenzothiophene. The complex emits the characteristic red luminescence of Eu³⁺ ion due to the ⁵D₀ → ⁷F_J (J = 0–4) transitions under 395 nm-light excitation with a luminescent quantum efficiency of 23%. Bright red light-emitting diodes (LEDs) were fabricated by coating the complex onto 395 nm-emitting InGaN chip. The results indicate that the complex may act as a red component in the fabrication of near UV-based white light-emitting diodes with high color-rendering index.     

First example of PMMA-supported and highly luminous color-purity red-light metallopolymer based on a tris-β-diketonate Zn2 +-Eu3 +-complex

Through the copolymerization of a complex monomer [Zn(L)(4-vinyl-Py)Eu(TTA)₃] (2; H₂L = N,N′-bis(salicylidene)cyclohexane-1.2-diamine; 4-vinyl-Py = 4-vinyl-pyridine and HTTA = 2-thenoyltrifluoroacetonate) with MMA (methyl methacrylate), the first example of PMMA-supported and highly luminous (Ф_Eu^L = 63.1%) color-purity red-light metallopolymer poly(MMA-co-2) based on a tris-β-diketonate Zn^2 +-Eu^3 +-complex is obtained.     

Monometallic and bimetallic europium(III) and terbium(III) complexes: Synthesis and luminescent properties

Eight new lanthanide complexes of the form Ln(L)₃bipy and [Ln(L)₃]₂bpm were synthesized (where L = 2,2,6,6-tetramethyl-3,5-heptanedione (tmh) and 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (tdh), bipy = 2,2′-bipyridine, bpm = 2,2′-bipyrimidine and Ln = Tb(III) or Eu(III)). The luminescent spectra are typical of Tb(III) and Eu(III) complexes with intense transitions at 545 nm for Tb(III) and 612 nm for the Eu(III) complexes. Energy gaps between the tmh 1 orbitals and the ⁰D_J manifold of Eu(III) are too large to give efficient energy transfer therefore emission spectra for Eu(tmh)₃bipy and [Eu(tmh)₃]₂bpm were not detected. Lifetimes are greatest for the Tb(III) complexes containing tmh terminal ligands while the longest lifetimes for the Eu(III) complexes occur with the tdh terminal ligands.     

Structure and luminescence properties of Eu3+ doped TiO2 nanocrystals and prolate nanospheroids synthesized by the hydrothermal processing

We report on a new approach to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids. They were synthesized by shape transformation of hydrothermally treated titania nanotubes at different pH and in the presence of Eu³⁺ ions. The use of nanotubes as a precursor to the synthesis of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids opens the possibility of overcoming the problems related to molecular precursors. The shapes and sizes of the nanotubes, Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids were characterized by transmission electron microscopy (TEM) technique. Crystal structures of the resultant powders were investigated by X-ray diffraction (XRD) analysis. The percentage ratio of Eu³⁺ to Ti⁴⁺ ions in doped nanocrystals was determined using inductively coupled plasma atomic emission spectroscopy. The optical characterization was done by using fluorescence and ultraviolet-visible reflection spectroscopies. An average size of faceted Eu³⁺ doped TiO₂ nanocrystals was 13 nm. The lateral dimensions of Eu³⁺ doped TiO₂ prolate nanospheroids varied from 14 to 20 nm, while the length varied from 40 to 80 nm, depending on precursor concentrations. The XRD patterns revealed the homogeneous anatase crystal phase of Eu³⁺ doped TiO₂ nanocrystals and prolate nanospheroids independently of the amount of dopant. A postsynthetic treatment (filtration or dialysis) was applied on the dispersions of the doped nanoparticles in order to study the influence of the dopant position on photoluminescence (PL) spectra. In the red spectral region, room temperature PL signals associated with ⁵D₀ → ⁷F_J (J = 1–4) transitions of Eu³⁺ were observed in all samples. The increased contribution of dopants from the interior region of dialyzed nanocrystals to photoluminescence was confirmed by the increase of R value.     

Synthesis and characterization of the crystalline powders on the basis of Lu2O3:Eu3+spherical submicron-sized particles

This study is devoted to the preparation of the crystalline powders on the basis of non-agglomerated monodisperse Lu₂O₃:Eu³⁺ spherical particles with the diameters in the range of 50–250 nm by the soft chemistry co-precipitation route. The influence of the synthesis parameters on control morphology, particles size and agglomeration in the final Lu₂O₃:Eu³⁺ powder was considered. Lu₂O₃:Eu³⁺ crystalline powders were characterized by means of electron microscopy methods (TEM, SEM), FT-IR spectroscopy, thermal analysis (TG-DTA) and X-ray diffractometry. The mechanisms of the precursor decomposition and crystallization at the temperatures ranging from 60 to 900 °C were discussed. It was shown that the powders obtained were characterized by the effective luminescence under X-ray excitation in λ = 575–725 nm spectral region corresponding to ⁵D₀ → ⁷F_J transitions (J = 0–4) of Eu³⁺ ions with a maximum at 612 nm and the luminescence intensity strongly depends on annealing temperature. The relative densities of the green-bodies on the basis of Lu₂O₃:Eu³⁺ powders were estimated and the sintering of compacts at the temperatures up to 1500 °C was studied.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Y(PO4)3 red phosphors

A series of red-emitting phosphors Eu³⁺-doped Sr₃Y(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Y(PO₄)₃:Eu³⁺ phosphors exhibit peaks associated with the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The integral intensity of the emission spectra of Sr₃Y_0.94(PO₄)₃:0.06Eu³⁺ phosphors excited at 392 nm is about 3.4 times higher than that of Y₂O₃:Eu³⁺ commercial red phosphor. The Commission Internationale de l’Eclairage chromaticity coordinates, the quantum efficiencies and decay times of the phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Y(PO₄)₃ phosphors are promising red-emitting phosphors pumped by near-UV light.     

Monodisperse nanospheres of yttrium oxysulfide: Synthesis,characterization, and luminescent properties

A red long-lasting phosphorescent material, monodisperse Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ nanospheres have been prepared successfully. Y(OH)(CO₃): Eu³⁺ nanospheres were firstly synthesized via an urea-based homogeneous precipitation technique to serve as the precursor. Nanospheres long-lasting phosphors Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ were obtained by calcinating the precursor in CS₂ atmosphere. XRD investigation shows a pure phase of Y₂O₂S, indicating no other impurity phase appeared. SEM observation reveals that the structures are nanosphere. The Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ nanospheres with particle size about 100–150 nm show uniform size and well-dispersed distribution. After irradiation by ultraviolet radiation with 325 nm for 5 min, the phosphor emitted red color long-lasting phosphorescence corresponding to typical emission of Eu³⁺ ion. The main emission peaks are ascribed to Eu³⁺ ions transition from ⁵D_J (J = 0, 1, 2) to ⁷F_J (J = 0, 1, 2, 3, 4). Both the PL spectra and luminance decay revealed that this phosphor had efficient luminescent and long-lasting properties. It was considered that the red-emitting long-lasting phosphorescence was due to the persistent energy transfer from the traps to the Ti⁴⁺ and Mg²⁺ ions.     

A novel Eu(III) –Ag(I) heterometallic coordination polymer based on planar hexanuclear heterometallic second building unit

A novel Eu(III)–Ag(I) coordination polymer [Eu₂Ag(μ₄-oPyIDC)₂(NO₃)(H₂O)]_n (H₃oPyIDC = 2-(pyridine-3-yl)-1H-imidzole-4,5-dicarboxylate, 1) was formed based on a planar hexanuclear heterometallic Eu₄Ag₂ secondary building unit. The planar hexanuclear secondary building blocks are interconnected to a 3D framework with pcu topology. The luminescence property of compound 1 is also investigated.     

Luminescent and structural properties of a Eu(III) complex: Formation of a one-dimensional array bridged by 2,2′-bipyrimidine

The previously reported monometallic Eu(III) complex Eu(hfa)₃bpm, where hfa = 1,1,1,5,5,5- hexafluoroacetylacetonate and bpm = 2,2′-bipyrimidine, shows characteristic emissions in the visible region associated with the 5D₀ → 7F_J (J = 0–4) transitions of the Eu(III) center. Lifetime measurements are fit to a mono-exponential and are inversely related to temperature. Crystals grown from slow diffusion of hexanes into an ethyl acetate solution of the complex yield an unusual one-dimensional array in which each Eu(III) complex is connected to another through bpm bridging units.     

First example of near-infrared (NIR) luminescent Yb4(Salen)4-containing metallopolymer through radical copolymerization with MMA (methyl methacrylate)

Through the radical copolymerization of MMA (methyl methacrylate) with a vinyl-containing complex monomer {[Yb₄(L)₂(HL)₂(μ₃-OH)₂(NO₃)₂]·(NO₃)₂} (1; H₂L = N,N′’-bis-(5-(3′-vinylphenyl)-3-methoxy-salicylidene)cyclohexane-1,2-diamine), the first example of PMMA-supported and Yb₄(Salen)₄-containing metallopolymer Poly(1-co-MMA) exhibits significantly improved physical properties besides relatively higher NIR quantum yields (Φ_Yb^Yb = 1.18% and Φ_L^Yb = 0.86%) than those (Φ_Yb^Yb = 1.02–1.04% and Φ_L^Yb = 0.73–0.75%) of complex monomer 1 in solution and 1@PMMA in solid state.     

Dual-nodal PMMA-supported Eu3 +-containing metallopolymer with high color-purity red luminescence

Based on chemical grafting of the complex monomer [Eu(TTA)₃(4-vinyl-Py)₂] (HTTA = 2-thenoyltrifluoroacetylacetate, 4-vinyl-Py = 4-vinyl-pyridine) with two active vinyl groups and MMA (methyl methacrylate), the dual-nodal PMMA-supported metallopolymers with high color-purity Eu^3 +-based luminescence are obtained. The physical properties show that their luminescent properties (τ_obs = 494–552 μs and Ф_Eu^L = 50–55%) are distinctively enhanced from copolymerization in comparison with those (τ_obs = 470 μs and Ф_Eu^L = 44%) of the complex monomer besides the improvement of thermal-stabilities.     

Improved photovoltaic performances of Ru (II) complex sensitized DSSCs by co-sensitization of carbazole based chromophores

Herein, we report photovoltaic performance studies of three carbazole based dyes (N_1–3) derived from (Z)-3-(9-hexyl-9H-carbazol-3-yl)-2-(thiophen-2-yl)acrylonitrile scaffold as effective co-sensitizers in Ru (II) complex, i.e. NCSU-10 sensitized DSSCs. From the results it is evident that, the device fabricated using co-sensitizer N₃ with 0.2 mM of NCSU-10 exhibited improved photon conversion efficiency (PCE) of 8.73% with J_SC of 19.87 mA·cm^− 2, V_OC of 0.655 V and FF of 67.0%, while N₁ displayed PCE of 8.29% with J_SC of 19.75 mA·cm^− 2, V_OC of 0.671 V and FF of 62.6%, whereas NCSU-10 (0.2 mM) alone displayed PCE of 8.25% with J_SC of 20.41 mA·cm^− 2, V_OC of 0.667 V and FF of 60.6%. However, their EIS studies confirm that, N₁, showing higher V_OC is efficient in suppressing the undesired charge recombination in DSSCs through enhanced surface coverage on TiO₂ and thereby resulting in longer electron lifetime than that of NCSU-10 dye alone. Here, the higher PCE of N₃ can be attributed to its improved light harvesting efficiency, which is due to the presence of highly electron withdrawing barbituric acid in its structure. Conclusively, the results showcase the potential of simple carbazole based dyes as co-sensitizers in improving efficiency of DSSCs.     

A four-spin ring with alternating magnetic interactions formed by pyridine-substituted nitronyl nitroxide radicals and Gd(III) ions: Crystal structure and magnetic properties

A novel complex, [Gd(hfac)₃(NIT-5-Br-3py)]₂ (hfac = hexafluoroacetylacetonat, NIT-5-Br-3py = 2-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)-5-bromo-3-pyridine) has been synthesized and characterized structurally and magnetically, in which a NIT-5-Br-3py molecular acts as a bridge ligand linking two Gd(III) ions through the oxygen atom of the N–O group and nitrogen atom from the pyridine ring to form a four-spin system. The fitting result of the magnetic susceptibility shows two different magnetic interactions between Gd(III) ion and NIT-5-Br-3py in one complex: a weak ferromagnetic interaction (J₁ = +2.60 cm⁻¹) through the N–O group, and a much weaker antiferromagnetic (J₂ = −0.24 cm⁻¹) interaction through pyridine ring.     

Pure white-light and color-tuning of PMMA-supported hybrid materials doped with (TTA)3-Zn2 +-Eu3 + and (BA)3-Zn2 +-Tb3 + complexes

Based on the doping of red-light-emitting 2 ([Zn(L)(4-vinyl-Py)Eu(TTA)₃]; H₂L = N,N′-bis(salicylidene)cyclohexane-1,2-diamine, 4-vinyl-Py = 4-vinyl-pyridine, HTTA = 2-thenoyltrifluoroacetonate) and cyan-light-emitting 4 ([Zn(L)(4-vinyl-Py)Tb(BA)₃]; HBA = 1-phenyl-1,3-butanedione) in PMMA, hybrid materials of 2@4@PMMA with improved physical properties including color-tunable for white-light (CIE coordinate 0.373, 0.319) were obtained.     

A single-phase white-emitting La10(SiO4)6O3：Eu2+/Eu3+ phosphor for near-UV LED-based application

A novel single-phase white-emitting phosphor La₁₀(SiO₄)₆O₃ (LSO): xEu has been synthesized by high-temperature solid-state reaction. Its crystal structure, luminescence properties, fluorescence decay time and oxygen vacancies have been characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. XRD result shows a typical oxyapatite structure with the space group of P6₃/m. Characteristic excitation and emission peaks of Eu²⁺ and Eu³⁺ were observed from PL studies. The optimum doping concentration of Eu was found to be 7.5 mol% (x = 0.075). In this work, the lifetimes of Eu³⁺ and Eu²⁺ were considerably longer than those from some references. Under the excitation of different near ultraviolet (n-UV) longer wavelengths (λex = 360, 370, and 380 nm), the white light emission can be realized with the CIE chromaticity coordinates (0.3907, 0.3595), (0.3472, 0.3282), and (0.3504, 0.3062) for the phosphor LSO: 0.075Eu. The chromaticity coordinates of the phosphor were all located in the white region. Therefore, it is suggested that the explored LSO: 0.075Eu phosphor can be a good candidate for white light-emitting diodes (W-LEDs) application.     

Preparation and photoluminescence properties of Eu3+-doped ZrO2 nanotube arrays

Zr–Eu alloy containing 3 at% Eu was prepared by a powder metallurgical method and Eu³⁺-doped ZrO₂ nanotube arrays were prepared by anodising the Zr–Eu alloy. The properties of Eu³⁺-doped ZrO₂ nanotube arrays were studied in contrast to undoped ZrO₂ nanotube arrays under different annealing temperatures. Results showed that the Eu³⁺ ions could not only stabilise the tetragonal phase of zirconium oxide, but also make the crystallite sizes smaller. Annealing temperature exerted a significant influence on the absorbance value, as well as the intensity and position of the photoluminescence peaks. When the excitation wavelength was either 248 nm or 270 nm, the sample annealed at 600 °C displayed the strongest emission peak; while under excitation at 232 nm, the sample annealed at 400 °C exhibited the strongest emission peak.     

Gel-combustion assisted synthesis of eulytite-type Sr3Y(PO4)3 as a single host for narrow-band Eu3+ and broad-band Eu2+ emissions

A series of eulytite-type Sr₃Y_1-x(PO₄)₃:xEu³⁺ (x = 0–0.13) and Sr_3-yY(PO₄)₃:yEu²⁺ (y = 0–0.10) phosphors were successfully synthesized via gel-combustion and subsequent calcination in O₂ and Ar/H₂ atmospheres at 1250 °C, respectively. Detailed crystal structure analysis via Rietveld refinement showed that the phosphors were crystallized in the cubic system (space group I-43d, No. 220), in which the Eu³⁺ and Eu²⁺ activators reside at the Y³⁺ and Sr²⁺ sites, respectively. The trivalent Eu³⁺ ions (CN = 6) exhibited typical narrow-band luminescence via intra-4f⁶ transitions, with the red emission at ~ 615 nm being dominant (⁵D₀ → ⁷F₂ transition, FWHM = 15.9 ± 0.2 nm). The divalent Eu²⁺ ions (CN = 6 and 9) showed broad-band luminescence ranging from light-blue to blue via 4f⁶5d¹ → 4f⁷ transitions (FWHM = 115 ± 2 nm). The optimal Eu³⁺ and Eu²⁺ concentrations were determined to be 10 at% (x = 0.10) and 7 at% (y = 0.07), respectively, and the mechanisms of concentration quenching were discussed. The excitation/emission properties, fluorescence decay kinetics, CIE chromaticity, and particularly the rarely addressed thermal stability of the phosphors were investigated in detail.