Optical properties of rare-earth doped epitaxial Sr0.5Ba0.5Nb2O6 thin films grown by pulsed laser deposition

Optical quality rare-earth (RE) (Nd³⁺, Eu³⁺, Gd³⁺ and Yb³⁺) doped Sr_0.5Ba_0.5Nb₂O₆ (SBN) epitaxial films of ~ 170 nm thick have been successfully grown on MgO (100) single crystal substrates using pulsed laser deposition technique. Strong residual stress in these films has been revealed by Raman spectroscopic studies. Two kinds of in-plane orientations with respect to the MgO substrate co-exist. All the film samples show high transparency in the visible wavelength. Their band-gap energies appear to be independent of the types of dopant. Photoluminescence (PL) spectra of RE-doped SBN ceramics show a strong and broad emission band at around 600 nm (2.07 eV). The peak position of this emission band changes slightly with different RE-dopants. Thin film samples, however, yield a broad PL band at around 385 nm (3.22 eV). This UV emission shows no observable shift in the peak position for different dopants. Apart from these broad emission bands, conspicuous emission lines from Eu³⁺ and Nd³⁺ ions are also noted. The origins of these PL spectra are discussed.     

Electronic structure and photoluminescence properties of Eu-activated Ca4Si2O7F2

The blue-emitting phosphors Ca_(4−x)Eu_xSi₂O₇F₂ (0 < x ? 0.05) have been prepared by solid-state reaction and the photoluminescence properties have been studied systematically. The electronic structure of calcium fluoride silicate Ca₄Si₂O₇F₂ was calculated using the CASTEP code. The calculation results of electronic structure show that Ca₄Si₂O₇F₂ has an indirect band gap with 5 eV. The top of the valence band is dominated by O 2p and Si 3p states, while the bottom of the conduction band is mainly composed of Ca 3d states. Under the 350 nm excitation, the obtained sample shows a broad emission band in the wavelength range of 400-500 nm with peaks of 413 nm and 460 nm from two different luminescence centers, respectively. The relative intensity of the two peaks changes with the alteration of the Eu²⁺ concentration. The strong excitation bands of the powder in the wavelength range of 200-420 nm are favorable properties for the application as lighting-emitting-diode conversion phosphor.     

Synthesis and luminescent properties of ZnNb2O6 nanocrystals for solar cell

The phase formation, morphology and luminescent properties of ZnNb₂O₆ nanocrystals by the sol-gel method were investigated at a lower temperature than that of the traditional solid-state reaction method. The products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), photoluminescence spectroscopy (PL) and absorption spectra. The activation energy of ZnNb₂O₆ grain growth is obtained about 18.4 kJ/mol. The diameters of the nanocrystals are in the range of 20-40 nm. The PL spectra excited at 276 nm have a broad and strong blue emission band maximum at 450 nm, corresponding to the self-activated luminescence of the niobate octahedra group [NbO₆]⁷⁻. The optical absorption spectrum of the sample at a calcination temperature of 800 °C has a band gap energy of 3.68 eV.     

Raman spectroscopy and cathodoluminescence characteristics of order-disorder Ba(Zn1/3Ta2/3)O3 ceramics

The order-disorder transition in Ba(Zn_1/3Ta_2/3)O₃ (BZT) was characterized by using Raman spectroscopy, transmission electron microscopy (TEM), and cathodoluminescence (CL) microscopy. The 1:2 ordered structure of pure BZT ceramics was replaced by a 1:1 ordered structure at 1650 °C and the 1:1 ordered structure of BZT sintered at 1650 °C exhibited a 1:2 ordered structure when it was reannealed at 1500 °C for 12 h. The A_1g lines in the Raman spectrum of the sintered and reannealed samples were shifted to lower and higher wavenumbers, respectively. From the CL analysis, the 1:1 ordered BZT exhibited mainly three emission bands at around 533.2 (2.32 eV), 599.1 (2.07 eV), and 682.1 nm (1.81 eV), whereas the 1:2 ordered BZT exhibited mainly five bands at 346.4 (3.58 eV), 427.5 (2.90 eV), 520.9 (2.38 eV), 593.0 (2.09 eV), and 678.9 nm (1.82 eV). The strongest band originating from 2.32 to 2.38 eV was broadened, and the band center shifted towards a higher and lower wavelength in the 1:1 and 1:2 ordered BZT, respectively. Additional bands at around 346 and 427 nm in the grain interior of the annealed sample were strongly related to the 1:2 ordering of BZT.     

Photoluminesence studies of CdTe/SnO2 and CdTe/CdS heterojunctions: The influence of oxygen and the CdCl2 heat treatment

The influence of oxygen and annealing in the presence of CdCl₂ on the photoluminescence (PL) spectra of CdTe, component of SnO₂/CdTe heterojunction (HJ), has been studied in a temperature range of 17-100 K. The changes in the photoluminescence spectra were studied as a function of excitation intensity. Analysis of the PL spectra was carried out with considerations of spectra obtained from CdS/CdTe heterojunctions. CdTe side PL (SnO₂/CdTe HJ) consisted of 1.450 eV-DA defect band and 1.243 eV band (17 K). Annealing resulted in the disappearance of 1.243 eV band in oxygen containing samples. Interface PL for the unannealed samples consisted of mainly the 1.264 eV and a trace of the defect band. The CdCl₂ treatment is responsible for an almost symmetrical 1.416 eV band.     

Photoluminescence properties of RE-activated Na3GdP2O8 (RE = Tb, Dy, Eu, Sm) under VUV excitation

RE³⁺-activated monoclinic Na₃GdP₂O₈ (RE³⁺ = Tb³⁺, Dy³⁺, Eu³⁺, Sm³⁺) phosphors have been synthesized by a solid-state reaction method. Their photoluminescence properties in the vacuum ultraviolet (VUV) region were investigated. By analyzing their excitation spectra, the host-related absorption band was determined to be around 166 nm. The f-d transition bands and the charge transfer bands for Na₃GdP₂O₈:RE³⁺ (RE³⁺ = Tb³⁺, Dy³⁺, Eu³⁺, Sm³⁺) were assigned and corroborated. For the sample Na₃GdP₂O₈:5%Tb³⁺, the strong bands at around 202 and 221 nm are assigned to the 4f-5d spin-allowed transitions and the weak band at 266 nm is related to the spin-forbidden transition of Tb³⁺. For Na₃GdP₂O₈:5%Dy³⁺, the broad band at 176 nm could be related to the f-d transitions of Dy³⁺ and the O²⁻ → Dy³⁺ charge transfer band (CTB) besides the host-related absorption. In the excitation spectrum of Eu³⁺ doped sample, the O²⁻ → Eu³⁺ CTB is observed to be at 245 nm. For the Sm³⁺ doped sample, the O²⁻ → Sm³⁺ CTB is not distinguished obviously and is overlapped with the host-related absorption band.     

Luminescence and Raman study of α-Bi2O3 ceramics

Cathodoluminescence in the scanning electron microscope and photoluminescence in a confocal microscope have been used to investigate the luminescence properties of the stable monoclinic α-phase of Bi₂O₃. Powders of this oxide have been sintered at temperatures of 500 °C and 750 °C in air or in nitrogen atmospheres. Spectra of the starting powder and of the samples treated at 500 °C show luminescence bands at 1.50 eV and 1.95 eV as well as a band at 2.1 eV, more prominent in nitrogen treated samples. Sintering at 750 °C leads to quenching of the 1.50 eV infrared emission and the formation of a broad band with emission above 3 eV. The evolution of Raman bands with the sintering treatments has also been investigated.     

Photoluminescence spectra of MnIn2S4

MnIn₂S₄ single crystals grown by the directional crystallization method were investigated by using the temperature and excitation power dependencies of photoluminescence (PL) spectra. PL spectra consist of one broad band resulting from donor-acceptor pair recombination. The analysis of the temperature quenching of the PL intensity yields one defect donor level with a thermal ionization energy of about 0.17 eV. The broad band of PL spectra indicates that radiative recombination is related to multiphonon optical processes. The energy of the involved phonon was found to be around 0.025 eV and the energy of the acceptor level is about 0.86 eV.     

Photoluminescence and preparation of ZnNb2O6 doped with Eu and Tm nanocrystals for solar cell

Synthesis and luminescence properties of Eu³⁺ and Tm³⁺-doped ZnNb₂O₆ nanocrystals by the sol–gel process were investigated. The products were characterized by differential thermal analysis (DTA), scanning electron microscopy (SEM), and photoluminescence spectroscopy (PL). ZnNb₂O₆:Eu³⁺ shows bright red luminescence with maximum peak at 613 nm attributed to ⁵D₀ → ⁷F₂ transition. The major blue emission peak of ZnNb₂O₆:Tm³⁺ was at 483 nm, corresponding to the transitions ¹G₄ → ³H₆. The optimum concentration of Eu³⁺ and Tm³⁺ showing the maximum PL intensity was 4 mol% and 1 mol%, respectively.     

Effects of gamma-irradiation on Al2O3 crystals grown under reducing atmosphere

Gamma-ray irradiation-induced color centers in Al₂O₃ crystals grown by temperature gradient techniques (TGT) under a strongly reducing atmosphere were studied. The transition F⁺ → F takes place during the irradiation process. Glow discharge mass spectroscopy (GDMS) and annealing treatments show that Fe³⁺ impurity ions are present in the crystals. A composite (F⁺-Fe³⁺) defect was presented to explain the origin of the 255 nm band absorption in the TGT-Al₂O₃ crystals.     

Hydrothermal synthesis and photoluminescence properties of Gd2Zr2O7:Tb phosphors

This paper presents hydrothermal synthesis, characterization, and photoluminescence (PL) properties of novel green-emitting phosphors, Gd₂Zr₂O₇:Tb³⁺. Their crystal structure, morphology and photoluminescence properties were investigated by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM) and fluorescence spectrophotometer. The results revealed that one-dimensional Gd₂Zr₂O₇:Tb³⁺ nanorods with diameter of about 30 nm and length of 150-300 nm were formed, and the products exhibited a fluorite-type structure. PL study revealed that Gd₂Zr₂O₇:Tb³⁺ phosphors presented dominant green emission luminescence, which was attributed to the transitions from ⁵D₄ excited states to ⁷F_J (J = 3-6) ground states of Tb³⁺. The luminescence intensity of Gd₂Zr₂O₇:Tb³⁺ with different Tb³⁺ concentration was also investigated and reported, and an obvious concentration quenching was observed when Tb³⁺ ion concentration was 5 at.%.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.     

Microscale meshes of Ti3O5 nano- and microfibers prepared via annealing of C-doped TiO2 thin films

A new technique to produce microscale Ti₃O₅ nano- and microfiber meshes is proposed. When a 3 wt% carbon-doped TiO₂ film on Si(1 0 0) was annealed at 1000 °C in wet nitrogen (0.8%H₂O), the amorphous TiO₂ phase gave rise to crystalline phases of λ-Ti₃O₅ (75%) and rutile + trace of TiO_2−xC_x (25%). From Raman and FTIR Spectroscopy results, it was concluded that rutile is formed at the inner layer located at the interface between the mesh and the Si that was located away from the surface such that the meshes of nano- and microfibers are predominantly composed of Ti₃O₅ grown from the reaction of rutile with Si to form Ti₃O₅ and SiO₂. On the other hand, it was noteworthy that the microscale mesh of nano- and microfibers showed increased photoluminescence compared with amorphous TiO₂. The PL spectrum which had a broad band in the visible spectrum, fitted as three broad Gaussian distributions centered at 571.6 nm (∼2.2 eV), 623.0 nm (∼2.0 eV) and 661.9 nm (∼1.9 eV).     

Vacuum ultraviolet excited photoluminescence properties of novel Na3Y9O3(BO3)8:Eu phosphor

The novel vacuum ultraviolet (VUV) excited Na₃Y₉O₃(BO₃)₈:Eu³⁺ red phosphor was synthesized and the photoluminescence (PL) properties were investigated. The phosphor showed strong VUV PL intensity, large quenching concentration (40 mol%) and good chromaticity (0.649, 0.351). The Eu³⁺-O²⁻ charge transition (CT) was observed to be at a higher energy (232 nm, 5.35 eV). The host absorption at 127-166 nm was broad and strong when monitoring the Eu³⁺ emission, which indicated that energy transfer from the host-lattice to the Eu³⁺ ions was efficient in Na₃Y₉O₃(BO₃)₈:Eu³⁺. These excellent VUV PL properties were revealed to be correlated with the unique isolated layer-type structure of Na₃Y₉O₃(BO₃)₈ host. The results showed that the Na₃Y₉O₃(BO₃)₈:Eu³⁺ would be a good candidate for VUV-excited red phosphor.     

Structural and optical studies of ZnS nanocrystal films prepared by sulfosalicylic acid (C7H6O6S)-assisted galvanostatic deposition with subsequent annealing

Zinc sulfide (ZnS) semiconductor nanocrystal films have been prepared on indium tin oxide coated glass substrates by sulfosalicylic acid (C₇H₆O₆S)-assisted galvanostatic deposition with subsequent annealing. The deposition was performed at 10 mA cm^− 2 in acidic electrolytes containing 15-30 mM Zn(CH₃COO)₂, 20 mM Na₂S₂O₃, 200 mM LiCl, 0.375 mM Na₂SO₃, and 0 or 0.2 mM C₇H₆O₆S. Results show that the presence of C₇H₆O₆S can suppress the precipitation of Zn and S impurity phases during the ZnS deposition process. As the [C₇H₆O₆S] = 0.2 mM and [Zn^2 +] = 20 mM, the deposited ZnS film exhibits only hexagonal structure with an ideal Zn/S atomic ratio of 1.03 and a close-packed granular morphology. But its band gap about 2.86 eV is narrower than the common value of ZnS, probably due to the existence of some spurious acetate species and defect states. By annealing the film at 400 °C for 60 min, its band gap increased up to 3.70 eV, despite that its crystalline phase transformed into cubic structure which usually shows the narrower band gap than hexagonal ZnS. The significant band gap widening could be ascribed to the degradation of spurious acetate species and the reduction of various possible defect states in the annealing process.     

Hydrothermal synthesis and luminescent properties of Y2O3:Tb and Gd2O3:Tb microrods

One-dimensional (1D) Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods have been successfully prepared through a large-scale and facile hydrothermal method followed by a subsequent calcination process in N₂/H₂ mixed atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (IR), thermogravimetric analysis (TGA), energy-dispersive X-ray spectra (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-formed products via the hydrothermal process could transform to cubic Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ with the same morphology and slight shrinking in size after a postannealing process. Both Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods exhibit strong green emission corresponding to ⁵D₄ → ⁷F₅ transition (542 nm) of Tb³⁺ under UV light excitation (307 and 258 nm, respectively), and low-voltage electron beam excitation (1.5 → 3.5 kV), which have potential applications in fluorescent lamps and field emission displays.     

Conversion of green emission into white light in Gd2O3 nanophosphors

Gd₂O₃ nanophosphors were prepared by combustion synthesis with and without doping of Dy³⁺ ions. The X-ray powder diffraction patterns indicate that as-prepared Gd₂O₃ and 0.1 mol% Dy₂O₃ doped Gd₂O₃ nanophosphors have monoclinic structures. The transmission electron microscope (TEM) studies revealed that the as-prepared phosphors had an average crystallite sizes around 37 nm. The excitation and emission properties have been investigated for Dy³⁺ doped and undoped Gd₂O₃ nanophosphors. New emission bands were observed in the visible region for Gd₂O₃ nanophosphors without any rare earth ion doping under different excitations. A tentative mechanism for the origin of luminescence from Gd₂O₃ host was discussed. Emission properties also measured for 0.1 mol% Dy³⁺ doped Gd₂O₃ nanophosphors and found the characteristic Dy³⁺ visible emissions at 489 and 580 nm due to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions, respectively. The chromaticity coordinates were calculated based on the emission spectra of Dy³⁺ doped and undoped Gd₂O₃ nanophosphors and analyzed with Commission Internationale de l'Eclairage (CIE) chromaticity diagram. These nanophosphors exhibit green color in undoped Gd₂O₃ and white color after adding 0.1 mol% Dy₂O₃ to Gd₂O₃ nanophosphors under UV excitation. These phosphors could be a promising phosphor for applications in flat panel displays.     

Optical and thermal analysis of ZnO-CdO-TeO2 glasses doped with Nd

It is presented the Nd doping of the glassy ZnO-CdO-TeO₂ ternary system. The Nd-doped oxide glasses were prepared by conventional melt-quenching method using three different compositions from this system. X-rays diffraction (XRD) diagrams in these materials reveal that they are basically vitreous structure. Infrared (IR) spectra of the glasses showed the characteristic bands at 665, 670, and 675 cm⁻¹, which correspond to the trigonal structure of TeO₃. The presence of Nd³⁺ was detected in the visible and infrared region of the spectra by optical absorption (OA) measurements of the band gap and by photoluminescence (PL) experiments. Glasses showed light emission due to the transition: ⁴F_3/2 → ⁴I_9/2. Differential thermal analysis (DTA) of these glasses have shown that T_g temperatures are in the 465-485 °C and T_c in the 800-1000 °C ranges.     

Preparation and luminescence properties of nanocrystalline La2O3:Eu phosphor

Powders La₂O₃ doped with 1 mol% Eu were prepared via a combustion route using different reducers (urea, glycine and citric acid). The structure and morphology were determined with XRD and HRTEM measurement. The main emission positions centered at 626 nm for ⁵D₀ → ⁷F₂ transition are observed. The variation of CT band with different reducers is observed. The intensity of ⁵D₀ → ⁷F₂ transition centered at 626 nm with respect to that of ⁵D₀ → ⁷F₁ transition is a function of the energy difference ΔE between the two CT band positions.     

Synthesis and crystal structure of triphosphate RbPrHP3O10

Crystals of RbPrHP₃O₁₀ have been grown by the flux technique and characterized by single-crystal X-ray diffraction. RbPrHP₃O₁₀ crystallizes in the triclinic space group with lattice parameters: a = 7.0655(5), b = 7.7791(4), c = 8.6828(6) Å, α = 74.074(3), β = 74.270(3), γ = 82.865(2)°, V = 441.09(5) ų, Z = 2. The crystal structure has been solved yielding a final R(F²) = 0.0443 and R_w(F²) = 0.1426 for 1955 independent reflections (F_o² ≥ 2σ(F_o²)). The structure of RbPrHP₃O₁₀ consists of PrO₈ polyhedra and P₃O₁₀⁵⁻ groups sharing oxygen atoms to form a two-dimensional framework; the PrO₈ polyhedra form infinite chains by edge-sharing. Each Rb⁺ ion is bonded to 10 oxygen atoms, these ions are located between chains formed of (HP₃O₁₀)⁴⁻. The energies of the vibrational modes of the crystal were obtained from measurements of the infrared spectrum.