Substitution effect of nitrogen atoms with carbon atoms in porphyrin on the electronic structure and excited states properties

Density functional theory (DFT) electronic structure calculations were carried out to predict the structures and the absorption and emission spectra for porphyrin and a series of carbaporphyrins-carbaporphyrin, adj-dicarbaporphyrin, opp-dicarbaporphyrin, tricarbaporphyrin and tetracarbaporphyrin. The ground- and excited-state geometries were optimized at the B3LYP/6-31g(d) and CIS/6-31g(d) level, respectively. The optimized ground-state geometry and absorption spectra of porphyrin, calculated by DFT and time-dependent DFT (TDDFT), are comparable with the available experimental values. Based on the optimized excited-state geometries obtained by CIS/6-31g(d) method, the emission properties are calculated using TDDFT method at the B3LYP/6-31g(d) level. The effects of the substitution of nitrogen atoms with carbon atoms at the center positions of porphyrin are discussed. The results indicate that the two-pyrrole nitrogens are important to the chemical and physical properties for porphyrin.

Effect of samarium on Mn activated zinc borosilicate storage glasses

Samarium and manganese co-doped zinc borosilicate storage glasses were prepared by high temperature solid state method. The effect of doping samarium on the defect of Mn activated sample was studied by means of thermoluminescence spectra. It was found that the shallower traps of the sample predominate with the addition of samarium, as a result, the phosphorescence and storage properties of the manganese doped zinc borosilicate glasses were greatly changed.

Patterning and photolumine scent properties of perovskite-type organic/inorganic hybrid luminescent films by soft lithography

Perovskite-type organic/inorganic hybrid layered compound (C6H5C2H4NH3)(2)PbI4 was synthesized. The patterning Of (C6H5C2H4NH3)(2)PbI4 thin films on silicon substrate was realized by the micromolding in capillaries (MIMIC) process, a kind of soft lithography. Bright green luminescent stripes with different widths (50, 15, 0.8 mum) have been obtained. The structure and optical properties Of (C6H5C2H4NH3)(2)PbI4 films were characterized by X-ray diffraction (XRD), UV/Vis absorption and photoluminescence excitation and emission spectra, respectively. It is shown that the organic-inorganic layered (C6H5C2H4NH3)(2)PbI4 film was c-axis oriented, paralleling to the substrate plane. Green exciton emission at 525 nm was observed in the film, and the explanations for it were given.

Luminescence and energy transfer of organically modified silica xerogels (OMSX) doped and undoped with Eu3+ and Tb3+

Organically modified silica xerogels (OMSX) and Eu3+ (Tb3+)-doped OMSX were prepared by the reaction of (3-aminopropyl) triethoxysilane (APS) with 3-isocyanatepropyltriethoxysilane (ICPTES) followed by the subsequent hydrolysis and condensation in the presence of Eu3+ (Tb3+) via sol-gel method, which were characterized by FT-IR, XRD, fluorescence excitation and emission spectra. The as-formed OMSX shows a strong blue emission with the maximum excitation and emission wavelength at 351 and 420 nm, respectively. Due to the spectral overlap between the emission band of OMSX and f-f absorption lines of Eu3+ and Tb3+ in the UV-blue region, an energy transfer was observed from OMSX host to Eu3+ and Tb3+ in OMSX/Eu3+ and OMSX/Tb3+, respectively. Excitation at 350-360 nm resulted in a very weak emission around 420 nm from OMSX host and strong emission of Eu3+ and Tb3+ in OMSX/Eu3+ and OMSX/Tb3+, respectively. The emission spectra of Eu3+ and Tb3+ consist of D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4) and D-5(4)-F-7(J) (J = 6, 5, 4, 3), respectively. Furthermore, the predicted structure of OMSX/Eu3+ and OMSX/Tb3+ is presented.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

Patterning and optical properties rhodamine B-doped organic-inorganic silica films fabricated by sol-gel soft lithography

Rhodamine B (RB)-doped organic-inorganic silica films and their patterning were fabricated by a sol-gel process combined with a soft lithography. The resulted film samples were characterized by atomic force microscope (AFM), optical microscope and UV/Vis absorption and photoluminescence excitation and emission spectra. The effects of the concentration of the RB dye and heat treatment temperature on the optical properties of the hybrid silica films have been studied. Four kinds of patterning structures with film line widths of 5, 10, 20 and 50 mum have been obtained by micromolding in capillaries by a soft lithography technique. The RB-doped hybrid silica films present a red color, with an excitation and emission bands around 564 and 585 mum, respectively. With increasing the RB concentration, the emission intensity of the RB-doped hybrid silica films increases and the emission maximum presents a red shift. The emission intensity of the films decreases with increasing the heat treatment temperatures.

Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Luminescence of the compounds Y0.5-xLi1.5VO4 :(Dy3+,Eu3+)

In this paper for the first time the compounds Y0.5-xLi1.5VO4:(Dy3+, Eu3+),(YLV:Dy,Eu) (0.01excitation and emission spectra were measured at room temperature. The blue, the yellow and the red emission from the F-4(9/2)-H-6(15/2) (474.2-484.2 nm) transitions and F-4(9/2)-H-6(13/2) (568-576.4 nm) transitions of Dy3+ and the D-5(0)-F-7(2) (608-619.2 nm) transitions of Eu3+, respectively, are very strong in multiwavelength.

Luminescent thin film of doped terbium complex obtained by sol-gel method

The transparent luminescent thin films of doped terbium complex were obtained by sol-gel method. The result indicates that rare earth carboxylates with poor solubility can be homogeneously doped into sol matrix in situ. The fluorescence spectra show that the thin film material emits the characteristic narrow band emission of Tb3+ under the UV excitation.

Synthesis, structure and luminescent properties of a new praseodymium(III) complex with beta-diketone

A new tetrakis praseodymium(tu) complex Pr(TFNB)(3)Phen has been synthesized, in which TFNB is 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione and Phen is 1,10-phenanthroline. Its crystal structure and luminescent spectra were successfully determined and investigated. The typical antenna effect existing in the luminescence of Pr(TFNB)(3)Phen was revealed by the study of the UV-Vis absorption spectra of ligands and the excitation spectrum of Pr(TFNB)(3)Phen.

Synthesis of the complex fluoride LiBaF3 and optical spectroscopy properties of LiBaF3 : M(M = Eu,Ce) through a solvothermal process

The complex fluoride LiBaF3 and LiBaF3:M(M = Eu, Ce) is solvothermally synthesized at 180 degreesC and characterized by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy. In the solvothermal process, the solvents, molar ratios of initial mixtures and reaction temperature play important roles in the formation of products. The excitation and emission spectra of the LiBaF3:M(M= Eu,Ce) have been measured by fluorescence spectrophotometer. In the LiBaF3: Eu emission spectra, there is one sharp line emission located at 360 nm arising from f --> f transition of Eu2+ in the host lattice, and typical doublet 5d-4f emission of Ce3+ in LiBaF3 powder is shown.

Novel indigo light emitting long-lasting phosphors CdSiO3: RE3+ (RE = Y, La, Gd, Lu)

A series of novel indigo light emitting long-lasting phosphors CdSiO3: RE3+ (RE = Y, La, Gd, Lu) was prepared by the conventional high-temperature solid-state method. The XRD, photoluminescence (PL) spectra and afterglow intensity decay were used to characterize the synthesized phosphors. These phosphors emitted indigo light and showed long-lasting phosphorescence. The phosphorescence can be seen with the naked eye in the dark clearly even after the 254-nm UV irradiation have been removed for more than 30 min.

Multi-color long-lasting phosphorescence of rare earth ions in CdSiO3 matrix

A series of rare earth ions doped CdSiO3:RE3+(RE=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) multi-color long-lasting phosphorescence phosphors are prepared by the conventional high-temperature solid-state method. The results of XRD measurement indicate that the products fired under 1050degreesC for 3 h have a good crystallization without any detectable amount of impurity phase. Rare earth ions doped CdSiO3 phosphors possess excellent luminescence properties. When rare earth ions such as Y3+, La3+, Gd3+, Lu3+, Ce3+, Nd3+, Ho3+, Er3+, Tm3+ and Yb3+ are introduced into the CdSiO3 host, one broadband centered at about 420 nm resulting from traps can be observed. In the case of other earth ions such as Pr3+, Sm3+, Eu3+, Tb3+ and Dy3+, their characteristic line emitting as well as the similar to420 nm broadband luminescence can be obtained. The mixture of their characteristic line emitting with the similar to420 nm broadband luminescence results in various afterglow color.

The optical spectroscopic properties of rare earth-activated barium orthophosphate in VUV-Vis range

The optical properties of rare earth ions-activated barium orthophosphate phosphors, Ba-3(PO4)(2):RE (RE = Ce3+, Sm3+, Eu3+, Eu2+, and Tb3+), were investigated in vacuum ultraviolet (VLTV)-Vis range. A band-band transition Of PO43- in Ba-3(PO4)(2) is observed in the region of 150-170 nm. The partial reduction of Eu3+ to Eu2+ was observed and confirmed by luminescent spectra under the VUV-UV excitation. It is proposed that the electronegative defects that formed by aliovalent substitution of Eu3+ on the Ba2+ site in the host are responsible for the reduction process.

Citrate-gel synthesis and luminescent properties of ZnGa2O4 doped with Mn2+ and EU3+

By using inorganic salts as raw materials and citric acid as complexing agent, spinel oxide ZnGa2O4 and Mn2+, Eu3+-doped ZnGa2O4 phosphor powders were prepared by a citrate-gel process. X-ray diffraction (XRD), TG-DTA, FT-IR. and luminescence excitation and emission spectra were used to characterize the resulting products. The results of XRD reveal that the powders begin to crystallize at 500 degreesC and pure ZnGa2O4 phase is obtained at 700 degreesC, which agrees well with the results of TG-DTA and FT-IR. In the crystalline ZnGa2O4, the Eu shows its characteristic red (615 nm, D-5(0)-F-7(2)) emission with a quenching concentration of 5 mol% (of Ga3+), and the Mn shows green emission (505 nm, T, A,) with a quenching concentration of 0.1 mol% (of Zn2+). The luminescence mechanism of ZnGa2O4:Mn2+/Eu3+ is presented.