Lanthanide absorption spectral probe in titania nanoparticles synthesized by ultrasonic assistant sol-gel method

Titania nanoparticles were obtained by an ultrasonic assistant sol-gel method. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermal analysis. The optical absorption of the samples has been measured by photoacoustic (PA) spectroscopy, which is powerful for detecting small amount of strongly scattering materials. The structural variations of the sample during the phase transitions were firstly studied using Nd³⁺ as an absorption spectral probe. The PA results show that the TiO₂ gel heated at 50 °C is basically amorphous and still contains abundant trapped water and ethanol, which makes the environment around Nd³⁺ similar with that of its aqueous ion. For the sample calcined at higher temperature, the f-f transitions of Nd³⁺ exhibit a continuous red shift along with the gel-to-anatase transformation, indicating an increase of the “degree of covalency” for Nd³⁺ bonding. For the sample calcined at 1100 °C, however, the f-f transitions of Nd³⁺ show blue shifts and the hypersensitive transition intensities of Nd³⁺ decrease, indicating an increase of ionicity for Nd³⁺ bonding. This can be attributed to the segregation of Nd³⁺ ions to the external surface, forming Nd₄Ti₉O₂₄ during the anatase-to-rutile transition.     

The effects of Li on the near-infrared luminescence properties of Nd/ Li codoped Y2O3 nanocrystals

Nd³⁺/ Li⁺ codoped Y₂O₃ nanocrystals were synthesized by glycine combustion method. The codoping of Li⁺ ions can lead to about twice enhancement of the near-infrared luminescence for the three spectral regions, which correspond to the ⁴F_3/2 → ⁴I_9/2, ⁴F_3/2 → ⁴I_11/2 and ⁴F_3/2 → ⁴I_13/2 channels of Nd³⁺. The enhancement could be attributed to the improved morphology, the modification of the local symmetry around Nd³⁺ ions and the reducing number of OH⁻ groups by codoping with Li⁺ ions.     

Efficient blue upconversion emission due to confined radiative energy transfer in Tm-Nd co-doped Ta2O5 waveguides under infrared-laser excitation

Intense blue upconversion emission at 480 nm has been obtained at room temperature in Tm³⁺-Nd³⁺ co-doped Ta₂O₅ channel waveguides fabricated on a Si substrate, when the sample is excited with an infrared laser at 793 nm. The upconversion mechanism is based on the radiative relaxation of the Nd³⁺ ions (⁴F_3/2 → ⁴I_11/2) at about 1064 nm followed by the absorption of the emitted photons by Tm³⁺ ions in the ³H₄ excited state. A coefficient of energy transfer rate as high as 3 × 10⁻¹⁶ cm³/s has been deduced using a rate equation analysis, which is the highest reported for Tm-Nd co-doped systems. The confinement of the 1064 nm emitted radiation in the waveguide structure is the main reason of the high energy transfer probability between Nd³⁺ and Tm³⁺ ions.     

Hydrothermal preparation and photoluminescent properties of MgAl2O4: Eu spinel nanocrystals

Nanoplates of the MgAl₂O₄ spinel doped with Eu³⁺ ions were prepared by a microwave assisted hydrothermal method. Structural properties of the precursor calcined at 700 and 1000 ^oC powders were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to the obtained XRD patterns the formation of single-phase spinels after calcination was confirmed. The average spinel particle size was determined to be 11 nm after calcination at 700 °C and it increased up to 14 nm after calcination at 1000 °C. The photoluminescent properties of prepared powders with different Eu³⁺ ion concentrations (0-5% mol) were investigated using excitation and emission spectroscopy at room and low temperatures (77 K).     

Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb sol gel derived phosphor

Terbium (1 mol%) doped ZnO-SiO₂ binary system was prepared by a sol-gel process. Nanoscopic effects of ZnO on the photoluminescence (PL) and the cathodoluminescence (CL) properties were studied. Defects emission from ZnO nanoparticles was measured at 560 nm and the line emission from Tb³⁺ ions in SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺ with a major peak at 542 nm was measured. The PL excitation wavelength for 542 nm Tb³⁺ emission was measured at ∼320 nm in both SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺. The CL data showed quenched luminescence of the ZnO nanoparticles at 560 nm from a composite of ZnO-SiO₂:Tb³⁺ and a subsequent increase in 542 nm emission from the Tb³⁺ ions. This suggests that energy was transferred from the ZnO nanoparticles to enhance the green emission of the Tb³⁺ ions. The PL and CL properties of ZnO-SiO₂:Tb³⁺ binary system and possible mechanism for energy transfer from the ZnO nanoparticles to Tb³⁺ ions are discussed.     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

Enhancing upconversion emissions of NaTm0.02YbxY0.98−xF4 nanocrystals through increasing Yb doping

By increasing the content of Yb³⁺ ions from 20% to 98% in NaTm_0.02Yb_xY_0.98−xF₄ (x=0.2−0.98) nanocrystals with size about 10 nm, the intensities of near infrared (800 nm) and blue (470 nm) upconversion (UC) luminescence can be enhanced by orders of 45 and 49 times, respectively, under 970 nm diode laser excitation. Pump power dependence illustrated that the 800 and 470 nm radiations are still two- and three-photon processes, respectively. TEM imaging showed that the enhancement is not from the change of the crystal size. Steady-state equation and the measured lifetimes indicated that the enhanced 800 nm radiations can induce the enhancement of the 470 nm emissions, which is in good agreement with the experimental data.     

Synthesis, characterization and optical properties of water-soluble ZnS:Mn nanoparticles

ZnS nanoparticles with Mn²⁺ doping (0.5-20%) have been prepared through a simple chemical method, namely the chemical precipitation method. The structure of the nanoparticles has been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV-vis spectrometer. The size of the particles is found to be 3-5 nm range. Photoluminescence spectra were recorded for undoped ZnS nanoparticles using an excitation wavelength of 320 nm, exhibiting an emission peak centered at around 445 nm. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn²⁺⁴T₁-⁶A₁ transition is observed along with the blue emission. The prepared Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission 580 nm with the blue emission suppressed. The maximum PL intensity is observed only at the excitation energy of 3.88 eV (320 nm). Increase in stabilizing time up to 48 h in de-ionized water yields the enhancement of emission intensity of doped (4% Mn²⁺) ZnS. The correlation made through the concentration of Mn²⁺ versus PL intensity resulted in opposite trend (mirror image) of blue and yellow emissions.     

Green synthesis and characterization of superparamagnetic Fe3O4 nanoparticles

In this paper, we have first demonstrated a facile and green synthetic approach for preparing superparamagnetic Fe₃O₄ nanoparticles using α-d-glucose as the reducing agent and gluconic acid (the oxidative product of glucose) as stabilizer and dispersant. The X-ray powder diffraction (XRD), X-ray photoelectron spectrometry (XPS), and selected area electron diffraction (SAED) results showed that the inverse spinel structure pure phase polycrystalline Fe₃O₄ was obtained. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results exhibited that Fe₃O₄ nanoparticles were roughly spherical shape and its average size was about 12.5 nm. The high-resolution TEM (HRTEM) result proved that the nanoparticles were structurally uniform with a lattice fringe spacing about 0.25 nm, which corresponded well with the values of 0.253 nm of the (3 1 1) lattice plane of the inverse spinel Fe₃O₄ obtained from the JCPDS database. The superconducting quantum interference device (SQUID) results revealed that the blocking temperature (T_b) was 190 K, and that the magnetic hysteresis loop at 300 K showed a saturation magnetization of 60.5 emu/g, and the absence of coercivity and remanence indicated that the as-synthesized Fe₃O₄ nanoparticles had superparamagnetic properties. Fourier transform infrared spectroscopy (FT-IR) spectrum displayed that the characteristic band of Fe-O at 569 cm⁻¹ was indicative of Fe₃O₄. This method might provide a new, mild, green, and economical concept for the synthesis of other nanomaterials.     

Upconverted 5d-4f luminescence from Er and Nd ions doped into fluoride hosts excited by ArF and KrF excimer lasers

We report on observation of upconverted VUV luminescence due to 5d-4f radiative transitions in Er³⁺ and Nd³⁺ ions doped into some fluoride crystals, under excitation by ArF and KrF excimer lasers, respectively. Only spin-forbidden 5d-4f luminescence of Er³⁺ (at 165 nm) was detected from the LiYF₄:Er³⁺ crystal whereas both spin-forbidden (at 169 nm) and spin-allowed (at 160.5 nm) components are observed from the BaY₂F₈:Er³⁺ crystal, the latter being much weaker than in the case of one-photon excitation. Nd³⁺ 5d-4f luminescence at 180 and 173 nm has been detected from the LiYF₄:Nd³⁺ and LaF₃:Nd³⁺ crystals, respectively. The shift of short-wavelength edge of 5d-4f emission spectra towards longer wavelengths is observed under temperature increase from 15 to 293 K. The observed effects in the spectra of Er³⁺ and Nd³⁺ doped crystals were interpreted as a result of reabsorption of 5d-4f luminescence escaping from the bulk of the crystals.     

Synthesis and characterization of BaAl2O4:Eu co-doped with different rare earth ions

Combustion method was used in this study to prepare BaAl₂O₄:Eu²⁺ phosphors co-doped with different trivalent rare-earths (Re³⁺=Dy³⁺, Nd³⁺, Gd³⁺, Sm³⁺, Ce³⁺, Er³⁺, Pr³⁺ and Tb³⁺) ions at an initiating temperature of 600 °C. The phosphors were annealed at 1000 °C for 3 h. As confirmed from the X-ray diffraction (XRD) data, both as prepared and post annealed samples crystallized in the well known hexagonal structure of BaAl₂O₄. All samples exhibited bluish-green emission associated with the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ at ∼500 nm. Although the highest intensity was observed from Er³⁺ co-doping, the longest afterglow (due to trapping and detrapping of charge carriers) was observed from Nd³⁺ followed by Dy³⁺ co-doping. The traps responsible for the long afterglow were studied using thermoluminescence (TL) spectroscopy.     

Optical properties of sol-gel fabricated Mn/SiO2 nanocomposites: Observation of surface plasmon resonance in Mn nanoparticles

Manganese nanoparticles were grown in silica glass and silica film on silicon substrate by annealing of the sol-gel prepared porous silicate matrices doped with manganese nitrate. Annealing of doped porous silicate matrices was performed at various conditions that allowed to obtain the nanocomposite glasses with various content of metallic Mn. TEM of Mn/SiO₂ glass indicates the bimodal size distribution of Mn nanoparticles with mean sizes of 10.5 nm and 21 nm. The absorption and photoluminescence spectra of Mn/SiO₂ glasses were measured. In the absorption spectra at 300 nm (4.13 eV) we observed the band attributed to the surface plasmon resonance in Mn nanoparticles. The spectra proved the creation of Mn²⁺ and Mn³⁺ ions in silica glass as well. The absorption spectra of Mn/SiO₂ glasses annealed in air prove the creation of manganese oxide Mn₂O₃. The measured reflection spectra of Mn/SiO₂ film manifest at 240-310 nm the peculiarity attributed to surface plasmons in Mn nanoparticles.     

Efficient fluorescence of dissolved CaF2:Tb and CaF2:Ce, Tb nanoparticles through surface coating sensitization

Oleic acid (OA)-modified CaF₂:Tb³⁺ nanoparticles with various Tb³⁺ concentrations and CaF₂:Ce³⁺, Tb³⁺ nanoparticles were synthesized. The as-prepared nanoparticles were shown to be well dissolved in some common organic solvents, such as chloroform and toluene. The nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray diffraction (XRD) and transmission electron microscopy (TEM). The investigation of fluorescence properties of CaF₂:Tb³⁺ nanoparticles showed that the Tb³⁺ ions could be sensitized efficiently by the surface coating of OA and CaF₂:Tb³⁺ nanoparticles with 10 mol% Tb³⁺ concentrations possess the highest emission intensity. The comparison of emission for CaF₂:Ce³⁺, Tb³⁺ and CaF₂:Tb³⁺ (10 mol%) nanoparticles revealed that the emission intensity of the former is about 4.5 times as strong as that of the latter.     

Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles

Rare earth doped NaLa(WO₄)₂ nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu³⁺-doped NaLa(WO₄)₂ nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu³⁺-doped NaLa(WO₄)₂ nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er³⁺ and 20 mol% Yb³⁺ codoped NaLa(WO₄)₂ nanoparticles under 980 nm excitation could also be observed. The Yb³⁺-Er³⁺ codoped NaLa(WO₄)₂ nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.     

Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.     

Enhanced near-infrared luminescence in Y2O3:Yb nanocrystals by codoping with Li ion

Y₂O₃:Yb³⁺ nanocrystals codoping with Li⁺ ions were synthesized by glycine combustion method. Codoping with Li⁺ ions leads to about 12 times enhancement of the photoluminescence (PL) intensity around 1 μm, in terms of the increased lifetimes at 1026 nm from 0.384 ms to 1.42 ms at room temperature. The enhancement in the PL intensity could be mostly attributed to the modification of the local symmetry around Yb³⁺ ions by codoping with Li⁺ ions.     

Investigations on structural and optical properties of Zn1−xGdxS nanoparticles

Zn_1−xGd_xS (x = 0.00, 0.02 and 0.04) nanoparticles were synthesized by facile chemical co-precipitation method using PVP as a surfactant. ZnS nanoparticles could be doped with Gd ions during synthesis without altering the XRD patterns of ZnS. Also, the pattern of the powders showed cubic zincblende structure. The particle size obtained from the XRD studies lies in the range 3-5 nm, whereas from TEM analysis it is 4 nm for x = 0.02 sample. The UV-Vis absorption spectra revealed that Zn_1−xGd_xS nanoparticles exhibit strong confinement effect as the blue shift in the absorption spectra with that of the undoped ZnS. The photoluminescence spectra showed enhanced luminescence intensity and the entry of Gd into host lattice.     

Upconverted VUV luminescence of Nd and Er doped into LiYF4 crystals under XeF-laser excitation

The upconverted VUV (185 nm) and UV (230 and 260 nm) luminescence due to 5d-4f radiative transitions in Nd³⁺ ions doped into a LiYF₄ crystal has been obtained under excitation by 351/353 nm radiation from a XeF excimer laser. The maximum upconversion efficiency, defined as the ratio of intensity for 5d-4f luminescence to overall intensity for 5d-4f and 4f-4f luminescence from the ⁴D_3/2 Nd³⁺ level, has been estimated to be about 70% under optimal focusing conditions for XeF laser radiation. A redistribution of intensity between three main components of 5d-4f Nd³⁺ luminescence is observed under changing the excitation power density, which favors the most long-wavelength band (260 nm) at higher excitation density level. The effect is interpreted as being due to excited state absorption of radiation emitted. The upconverted VUV and UV luminescence from the high-lying ²F(2)_7/2 4f level of Er³⁺ doped into a LiYF₄ crystal has also been obtained under XeF-laser excitation the most intense line being at 280 nm from the spin-allowed transition to the ²H(2)_11/2 4f level of Er³⁺, but the efficiency of upconversion for Er³⁺ emission is low, less than 5%.     

Eu/Tb ions co-doped white light luminescence Y2O3 phosphors

Y₂O₃:Eu³⁺, Tb³⁺ phosphors with white emission are prepared with different doping concentration of Eu³⁺ and Tb³⁺ ions and synthesizing temperatures from 750 to 950 °C by the co-precipitation method. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the crystallinity of the synthesized samples increases with enhancing the firing temperature. The photoluminescence spectra indicate the Eu³⁺ and Tb³⁺ co-doped Y₂O₃ phosphors show five main emission peaks: three at 590, 611 and 629 nm originate from Eu³⁺ and two at 481 and 541 nm originate from Tb³⁺, under excitation of 250-320 nm irradition. The white light luminescence color could be changed by varying the excitation wavelength. Different concentrations of Eu³⁺ and Tb³⁺ ions were induced into the Y₂O₃ lattice and the energy transfer from Tb³⁺→Eu³⁺ ions in these phosphors was found. The Commission International de l’Eclairage (CIE) chromaticity shows that the Y₂O₃:Eu³⁺, Tb³⁺ phosphors can obtain an intense white emission.     

Improved color purity in nano-size Eu-doped YBO3 red phosphor

Nano-size YBO₃:Eu³⁺ phosphor has been synthesized by the co-precipitation method. X-ray diffraction (XRD) pattern confirmed the formation of hexagonal vaterite-type structures of YBO₃:Eu³⁺ nanoparticles. The transmission electron microscopy (TEM) study revealed the formation of spherical YBO₃:Eu³⁺ nanoparticles with size 20-40 nm. The photoluminescence spectra revealed that the ratio of the red emission (⁵D₀-⁷F₂) to the orange emission (⁵D₀-⁷F₁) was much higher in the synthesized nano-size YBO₃:Eu³⁺ phosphor. The improved relative intensity, i.e., higher R/O value of emission peaks, is due to a lower symmetry of crystal field around Eu³⁺ ions.