Four New Lanthanide-Nitronyl Nitroxide (Ln(III)=Pr-III, Sm-III, Eu-III, Tm-III) Complexes and a Tb-III Complex Exhibiting Single-Molecule Magnet Behavior

Five new complexes based on rare-earth-radical [Ln(hfac)(3)(NIT-5-Br-3py)](2) (Ln=Pr (1), Sm (2), Eu (3), Tb (4), Tm (5); hfac = hexafluoroacetylacetonate; NIT-5-Br-3py = 2-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)-5-bromo-3-pyridine) have been synthesized and characterized by X-ray crystal diffraction. The single-crystal structures show that these complexes have similar structures, in which a NIT-5-Br-3py molecule acts as a bridging ligand linking two Ln(III) ions through the oxygen atom of the N-O group and nitrogen atom from the pyridine ring to form a four-spin system. Both static and dynamic magnetic properties were measured for complex 4, which exhibits single-molecule magnetism behavior.

Nanocrystalline LaAlO3:Sm3+ as a Promising Yellow Phosphor for Field Emission Displays

Nanocyrstalline LaAlO3:Sm3+ phosphors were prepared through a Pechini-type sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence, and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphors. XRD results reveal that the sample begins to crystallize at 600 degrees C, and pure LaAlO3 phase can be obtained at 700 degrees C. FE-SEM images indicate that the Sm3+-doped LaAlO3 phosphors are composed of aggregated spherical particles with sizes ranging from 40 to 80 nm. Under the excitation of UV light (245 nm) and low-voltage electron beams (1-3 kV), the Sm3+-doped LaAlO3 phosphors show the characteristic emissions of the Sm3+ ((4)G(5/2)-H-6(5/2), H-6(7/2), H-6(9/2) transitions) with a yellow color. The CL intensity (brightness) of the Sm3+-doped LaAlO3 phosphor is higher than that of the commercial product [Zn(Cd)S:Ag+] (yellow) to some extent.

Growth of highly crystalline CaMoO4 : Tb3+ phosphor layers on spherical SiO2 particles via sol-gel process: Structural characterization and luminescent properties

Highly crystalline CaMoO4:Tb3+ phosphor layers were grown on monodisperse SiO2 particles through a simple sol-gel method, resulting in formation of core-shell structured SiO2@CaMoO4:Tb3+ submicrospheres. The resulting SiO2@CaMoO4: Tb3+ core-shell particles were fully characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), and kinetic decays. The XRD results demonstrate that the CaMoO4:Tb3+ layers begin to crystallize on the SiO2 spheres after annealing at 400 degrees C and the crystallinity increases with raising the annealing temperature. SEM and TEM analysis indicates that the obtained submicrospheres have a uniform size distribution and obvious core-shell structure. SiO2@CaMoO4:Tb3+ submicrospheres show strong green emission under short ultraviolet (260 nm) and low-voltage electron beam (1-3 kV) excitation, and the emission spectra are dominated by a D-5(4) -F-7(5) transition of Tb3+(544 nm, green) from the CaMoO4:Tb3+ shells.

Nanocrystalline LaGaO3 : Tm3+ as an efficient blue phosphor for field emission displays with high color purity

Nanocrystalline Tm3+-doped LaGaO3 phosphors were prepared through a Pechini-type sol-gel process [M. P. Pechini, U.S. Patent No. 3,330,697 (11 July 1967)]. X-ray diffraction, field emission scanning electron microscopy, photoluminescence, and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphors. Under the excitation of ultraviolet light and low voltage electron beams (0.5-3 kV), the Tm3+-doped LaGaO3 phosphors show the characteristic emissions from the LaGaO3 host lattice and the Tm3+ (D-1(2), (1)G(4)-F-3(4), and H-3(6) transitions), respectively. The blue CL of the Tm3+-doped LaGaO3 phosphors, with a dominant wavelength of 458 nm, had better Commission International I'Eclairage chromaticity coordinates (0.1552, 0.0630) and higher emission intensity than the commercial product (Y2SiO5:Ce3+).

Sol-gel synthesis and characterization of SiO2@NaGd(WO4)(2): Eu3+ core-shell-structured spherical phosphor particles

Monodisperse, core-shell-structured SiO2@NaGd(WO4)(2):Eu3+ particles were prepared by the sol-gel method. The samples were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence (PL), and low-voltage cathodoluminescence (CL) as well as time-resolved PL spectra and lifetimes. PL and CL study revealed that the core-shell-structured SiO2@NaGd (WO4)(2):Eu3+ particles show strong red emission dominated by the D-5(0) - F-7(2) transition of Eu3+ at 614 nm with a lifetime of 0.74 ms. The PL and CL emission intensity can be tuned by the coating number of NaGd(WO4)(2):Eu3+ phosphor layers on SiO2 and by accelerating voltage and the filament current, respectively.

Pechini sol-gel deposition and luminescent properties of SrLa1-xRExGa3O7 (RE = Eu, Tb) phosphor films

SrLa1-xRExGa3O7 (RE = EU3+, Tb3+) phosphor films were deposited on quartz glass substrates by a simple Pechim sol-gel method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy, field-emission scanning electron microscopy, photoluminescence spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 700 degrees C and crystallized fully at 900 degrees C. The results of FNR spectra were in agreement with those of XRD. Uniform and crack-free films annealed at 900 degrees C were obtained with average grain size of 80 nm, root mean square roughness of 46 nm and thickness of 130 nm The RE ions showed their characteristic emission in crystalline SrLa1-xRExGa3O7 films, i.e., Eu3+ D-0-F-7(J) (J = 0, 1, 2, 3, 4), Tb3+5D4 -(7) F-J (J = 6, 5, 4, 3) emissions, respectively. The optimum concentrations (x) of Eu3+ and Tb3+ were determined to be 50, and 80 mol% in SrLa(1-x)RE(x)GGa(3)O(7) films, respectively.

Photoluminescence and electroluminescence properties of a samarium complex Sm(TTA)(3)phen

The photoluminescence (PL) and electroluminescence (EL) properties of a samarium complex Sm(TTA)(3)phen (TTA = 2-thenoyltri-fluoroacetonate, phen = 1, 10-phenanthroline) were investigated. The results show that Sm(TTA)3phen could be used as promising luminescent and electron transporting material in the electroluminescent devices. The difference between PL and EL spectra was noticed and discussed. Besides, it is noteworthy that the choice of the hole transporting layer (HTL) showed significant effect on the device performance, which was explained by the low-lying highest occupied molecular orbit (HOMO) level of Sm(TTA)3phen and the different hole injection barrier at the HTL/EML (emitting material layer) interface.

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

Thermoluminescence properties of Ce3+-doped LiSr4(BO3)(3) phosphor

Borates LiSr4(BO3)(3) were synthesized by high-temperature solid-state reaction. The thermoluminescence (TL) and some of the dosimetric characteristics of Ce3+-activated LiSr4(BO3)(3) were reported. The TL glow curve is composed of only one peak located at about 209 degrees C between room temperature and 500 degrees C. The Optimum Ce3+ concentration is 1 mol% to obtain the highest TL intensity. The TL kinetic parameters of LiSr4(BO3)(3):0.01Ce(3+) were studied by the peak shape method. The TL dose response is linear in the protection dose ranging from 1 mGy to 1 Gy. The three-dimensional thermoluminescence emission spectra were also studied, peaking at 441 and 474 nm due to the characteristic transition of Ce3+.

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4: Eu3+

It has been found that charge compensated CaMoO4:Eu3+ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO4:Eu3+ without charge compensation. Two approaches to charge compensation, (a) 2Ca(2+) -> EU3+ + M+, where M+ is a monovalent cation like Li+, Na+ and K+ acting as a charge compensator; (b) 3Ca(2+) -> 2EU(3+) + vacancy, are investigated. The influence of sintering temperature and Eu3+ concentration on the luminescent property of phosphor samples is also discussed.

Reduction from Eu3+ to Eu2+ in BaAl2O4 : Eu phosphor prepared in an oxidizing atmosphere and luminescent properties of BaAl2O4 : Eu

A reduction phenomenon of Eu3+ -> Eu2+ was observed for the first time when Eu3+ ions were doped into an AlO4-tetrahedron-containing compound BaAl2O4 in an oxidizing atmosphere of air by high-temperature solid-state reaction. X-ray powder diffraction patterns and photoluminescent spectra are used to confirm the compound structure and detect the simultaneous existence of both divalent and trivalent europium ions, respectively. The abnormal Eu3+ -> Eu2+ reduction is explained by a charge compensation model. Spectroscopic properties of BaAl2O4:Eu are discussed and Eu2+ emission spectrum shows consistence with the results reported by Katsumata et a]. [J. Cryst. Growth 198/199 (1999) 869.] and Lin et al. [Mater. Chem. Phys. 70 (2001) 156.].

Pr~(3+)或Sm~(3+)掺杂YAG∶Ce的发光特性及其荧光寿命

研究了Pr3+,Sm3+掺杂对YAG∶Ce发射光谱及其荧光寿命的影响。观察到当掺杂Pr3+时,在609nm处出现Pr3+的发射峰,而掺杂Sm3+时,在616nm处呈现Sm3+的发射峰。掺杂Pr3+或Sm3+增加红光区的发射峰将有利于提高YAG∶Ce荧光粉的显色性。实验中测定了(Y0.95Sm0.01Ce0.04)3Al5O12、(Y0.95Pr0.01Ce0.04)3Al5O12、(Y0.96Ce0.04)3Al5O12的荧光寿命(τ),观察到在YAG∶Ce中掺入Pr3+或Sm3+使Ce3+的荧光寿命减小。实验结果表明,少量掺杂Pr3+或Sm3+并未引起基质的结构的变化。

Structure and electrical properties of Pr ans Sm doped CeO2 and Ce2MoO15 based solid electrolytes

Sin and Pr doped CeO2 and Ce6MoO15 based materials were synthesized by sol-gel method. The structure of the powders were characterized by X-ray diffraction (XRD), Raman spectra, field emission scanning electron microscopy(FE-SEM) and the electrical conductivity of the samples was investigated by AC impedance spectroscopy. By comparing the structure and electrical properties of different systems, it could be concluded that the electrical property of Ce6MoO15 based system is better than that of CeO2 system. The added Mo element resulted in the increase of gain size and improved the grain boundary conductivity notably below 600 degrees C, while the Pr dopant induced the smaller grain size and improved the grain boundary conductivity of the materials.

Phase conversion and spectral properties of long lasting phosphor Zn-3 (PO4)(2): Mn2+, Ga3+

A red long lasting phosphor Zn-3(PO4)(2): Mn2+ Ga3+ (ZPMG) was prepared by ceramic method, and phase conversion and spectral properties were investigated. Results indicated that the phase conversion from alpha-Zn-3(PO4), beta-Zn-3(PO4)(2) to gamma-Zn-3(PO4)(2) occurs with different manganese concentration incorporated and sinter process. The structural change induced by the phase transformation results in a remarkable difference in the spectral properties. The possible luminescence mechanism for this red LLP with different forms has been illustrated.

Synthesis and photoluminescence of the Y2O3 : Eu3+ phosphor nanowires in AAO template

The monodisperse array and nanowires Of Y2O3:Eu3+ phosphor were synthesized using anodic aluminum oxide (AAO) template by sol-gel method. Scanning electron microscope (SEM) images indicated that Y2O3:Eu3+ nanowires are parallelly arranged, all of which are in uniform diameter of about 50 nm. The high-magnification SEM image showed that each nanowire is composed of a lot of agglutinating particles. The patterns of selected-area electron diffraction confirmed that Y2O3:EU3+ nanowires mainly consist of polycrystalline materials. Excitation and emission spectra Of Y2O3:E U3+/AAO composite films were measured. The characteristic red emission peak of EU3+ ion attributed to D-5(0)-->F-7(2) transition in Y2O3:EU3+/AAO nanowires broadened its halfwidth.