Emission properties of (SrTiO3-TiO2):Pr eutectic with self-organized fractal microstructure

An investigation of spectroscopic properties of (SrTiO₃-TiO₂):Pr³⁺ eutectic and, for comparison, of bulk SrTiO₃:Pr³⁺ and TiO₂:Pr³⁺crystals is presented. Luminescence spectra have been measured under both 450 nm and 350 nm excitation wavelength. For UV excitation they are characterized by a dominant red luminescence corresponding to transition from the ¹D₂ level of Pr³⁺ ions. The mechanism responsible for quenching of blue (from ³P₀ state) and intensification of red luminescence is proposed to be thermally-induced radiationless relaxation involving a low-lying Pr³⁺-Ti⁴⁺ intervalence charge transfer state. Measured decay constants of ¹D₂ excited state of Pr³⁺ are compared with values obtained for other praseodymium doped titanate hosts.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Photoluminescence characteristics of Li-doped CaTiO3:Pr thin films grown on Si (100) substrate by PLD

The effects of Li-doped CaTiO₃:Pr³⁺ thin films have been investigated by varying the lithium ion concentrations from 0 to 5 wt.%. The films have been deposited on Si (100) substrate using a pulsed laser deposition technique. Structural properties of these films have been studied by the measurement of their XRD, SEM, and AFM. The variation of Li⁺ concentration influences the crystallinity and surface morphology of the CaTiO₃:Pr³⁺ thin films. As Li⁺ content increases from 0 to 1 wt.%, the crystallinity and intensity of emission increases. The dominant emission is from ¹D₂ → ³H₄ transition at 613 nm. The ¹D₂ emission quenching has also been observed in highly doped sample and is related to the cross-relaxation process between Pr³⁺ ions.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

The influence of the Pr 4f5d configuration on the S0 emission efficiency and lifetime in LaPO4

The photoluminescence and excitation spectra of Pr³⁺ activated LaPO₄ has been investigated in the 1.6-300 K temperature region. At room temperature, the luminescence of LaPO₄:Pr³⁺ is composed of the interconfigurational 4f¹5d¹ → 4f² emission transitions. However, in the 1.6-60 K temperature range, the emission spectrum also consists of the intraconfigurational emission transitions that emanate from the ¹S₀ state. A radiative lifetime of 145 ns is measured for the Pr³⁺¹S₀ → ¹I₆ emission transition in LaPO₄. This is one of the shortest radiative lifetime observed for this transition in a solid. The energy position of the Pr³⁺¹S₀ state in LaPO₄ is established by high-resolution emission spectrum at 46 375 ± 5 cm⁻¹. A detailed analysis of the thermal quenching of the ¹S₀ lifetime and emission intensity is presented. It is proposed that the lowest energy state of the relaxed 4f¹5d¹ configuration is situated energetically below that of the ¹S₀ state.     

Enhanced photoluminescence of CaTiO3:Pr phosphor films deposited on SiO2 buffered Si substrates

CaTiO₃:Pr³⁺ films have been prepared by pulsed-laser deposition method on SiO₂-buffered Si substrates, and their microstructure and photoluminescence properties have been compared with those of the films deposited directly on bare Si substrates. The SiO₂ buffer layers were prepared using thermal oxidization and HF-etching. Photoluminescence intensities of CaTiO₃:Pr³⁺ films on the SiO₂-buffered Si substrates are significantly higher (up to 800%) than those of the films on bare Si substrates, which is attributed to the low refractive index and low light absorption of the SiO₂ buffer layer. This study reveals that the presence of the buffer layer is effective in improving the red emission brightness of CaTiO₃:Pr³⁺ films without sacrificing the surface roughness.     

Structure and magnetic property of CoFe2−xSmxO4 (x = 0–0.2) nanofibers prepared by sol–gel route

CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers with diameters about 100–300 nm have been prepared using the organic gel-thermal decomposition method. The composition, structure and magnetic properties of the CoFe_2−xSm_xO₄ nanofibers were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, inductive coupling plasma mass analyzer and vibrating sample magnetometer. The CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers obtained at 500–700 °C are of a single spinel structure. But, at 800 °C with a relatively high Sm content of 0.15–0.2 the spinel CoFe_2−xSm_xO₄ ferrite is unstable and the second phase of perovskite SmFeO₃ occurs. The crystalline grain sizes of the CoFe_2−xSm_xO₄ nanofibers decrease with Sm contents, while increase with the calcination temperature. This grain reduction effect of the Sm³⁺ ions doping is largely owing to the lattice strain and stress induced by the substitution of Fe³⁺ ions with larger Sm³⁺ ions in the ferrite. The saturation magnetization and coercivity increase with the crystallite size in the range of 8.8–57.3 nm, while decrease with the Sm content from 0 to 0.2 owing to a smaller magnetic moment of Sm³⁺ ions. The perovskite SmFeO₃ in the composite nanofibers may contribute to a high coercivity due to the interface pinning, lattice distortion and stress in the ferrite grain boundary fixing and hindering the domain wall motion.     

Fast d-f emission in Ce, Pr and Nd activated RbCl

In the search for new scintillator materials, Ce³⁺ doped chlorides are a promising class of materials, combining a high efficiency and fast response time. Even shorter response times may be achieved by replacing Ce³⁺ by Pr³⁺ or Nd³⁺ as the lifetime of the d-f emission is substantially shorter for these ions. Here we report on the luminescence properties of Ce³⁺, Pr³⁺ and Nd³⁺ in RbCl and investigate the potential as a scintillator material. Under UV excitation Ce³⁺ shows d-f emission between 325 and 425 nm. The emission originates from multiple (differently charge compensated) Ce³⁺ sites. The luminescence lifetime varies with wavelength and is ∼40 ns for the longer wavelength emission. For RbCl:Pr³⁺ three d-f emission band are observed between 250 and 350 nm which can be assigned to transitions from the lowest energy fd state to different ³H_J (J = 4-6) states within the 4f² configuration of Pr³⁺. The decay time is ∼17 ns. For the Nd³⁺ activated sample a weak emission band around 220 nm is observed only at 8 K which may be due to d-f emission. The very short lifetime (4 ns) is faster than the radiative lifetime, indicating that the d-f emission is quenched by relaxation to lower lying 4f³ states or by the process of photoionization. Under VUV excitation at wavelengths below 175 nm (the bandgap of RbCl) the d-f emission is very weak for Ce³⁺, Pr³⁺ and Nd³⁺ doped RbCl and the emission spectra are dominated by defect related emission. This indicates that energy transfer from the host lattice to the fd states is inefficient which prevents application as a scintillator material.     

Luminescence properties of Eu ions doped in Y2−xGdxO3 thin films grown by pulsed laser deposition method

Luminescence properties of Y_2−xGd_xO₃:Eu³⁺ (x = 0 to 2.0) thin films are investigated by site-selective laser excitation spectroscopy. The films were grown by pulsed laser deposition method on SiO₂ (100) substrates. Cubic phase Y₂O₃ and Gd₂O₃ and monoclinic phase Gd₂O₃ are identified in the excitation spectrum of the ⁷F₀ → ⁵D₀ transition of Eu³⁺. The emission spectra of the ⁵D₀ → ⁷F_J (J = 1 and 2) transition from individual Eu³⁺ centers were obtained by tuning the laser to resonance with each excitation line. The excitation line at around 580.60 nm corresponds to the line from Eu³⁺ with C₂ site symmetry of cubic phase. New lines at 578.65 and 582.02 nm for the C_S sites of Gd₂O₃ with monoclinic phase are observed by the incorporation of Gd in Y₂O₃ lattice. Energy transfer occurs between Eu³⁺ ions at the C_S sites and from Eu³⁺ ions at the C_S sites to those at the C₂ site in Y_2−xGd_xO₃.     

Electrical properties of lead-free thick film NTC thermistors based on perovskite-type BaCoxCo2xBi1 − 3xO3

Lead-free thick film negative temperature coefficient (NTC) thermistors based on perovskite-type BaCo^II_xCo^III_2xBi_1 − 3xO₃ (x ≤ 0.1) were prepared by mature screen-printing technology. The microstructures of the thick films sintered at 720 °C were examined by X-ray diffraction and scanning electron microscopy. The electrical properties were analyzed by measuring the resistance-temperature characteristics. For the BaBiO₃ thick films, the room-temperature resistivity is 0.22 MΩ cm, while the room-temperature resistivity is sharply decreased to about 3 Ω cm by replacing of Bi with a small amount of Co. For compositions 0.02 ≤ x ≤ 0.1, the values of room-temperature resistivity (ρ₂₃), thermistor constant (B_25/85) and activation energy are in the range of 1.995-2.975 Ω cm, 1140-1234 K and 0.102-0.111 eV, respectively.     

Effect of praseodymium substitution on the growth and properties of Y1−x Pr x Ba2Cu3O7−δ (o <x < 0·4) single crystals

In the present paper, a modified self-flux technique has been successfully employed for the growth of pure and praseodymium substituted (partially) large single crystals of high temperature superconducting Y_1−x Pr _x Ba₂Cu₃O_7−δ (x = 0·0,0·2,0·4). Typical sizes of the platy and bulky crystals of pure YBCO(123) material are ≈ 2 × 2 × 0·1 mm³ and 4 × 1 × 1 mm³, respectively. In case of Pr-substitution, the typical sizes of platy and bulky crystals of Y_0·8Pr_0·2Ba₂Cu₃O_7−δ and Y_0·6Pr_0·4Ba₂Cu₃O_7−δ materials are ≈ 2 × 3 × 0·1 mm³ and 5 × 1 × 1 mm³ and ≈ 1 × 1·5 × 0·1 mm³ and 7 × 0·2 × 0·1 mm³, respectively. The morphology and growth habit of the as-grown single crystals and the critical transition temperature (T _c) of the oxygenated crystals were found to depend on the Pr-content. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Ytterbium sensitization in KY3F10: Pr, Yb for silicon solar cells efficiency enhancement

The codoping of KY₃F₁₀ with Pr³⁺ and Yb³⁺ ions is investigated as a possible quantum cutting system to enhance solar cells efficiency. For one visible photon absorbed by Pr ions, two ytterbium ions are expected to be excited by two consecutive energy transfers. The subsequent emission of two infrared photons reduces thus the thermalization losses usually observed in Si solar cells. Emission spectra and lifetime decays in KY₃F₁₀ doped with 0.5% Pr³⁺ and codoped with 0%, 1%, 10% and 20% Yb³⁺ show an increase of the energy transfer efficiency from Pr³⁺ to Yb³⁺ with the Yb³⁺ concentration. For the first Pr³⁺ to Yb³⁺ energy transfer, an efficiency close to 100% is achieved in KY₃F₁₀: 0.5%Pr³⁺, 20%Yb³⁺. However, this promising result faces challenging issues since an increase in Yb concentration induces energy migration between Yb³⁺ ions which impairs the Yb³⁺ luminescence.     

Influence of Structural Effects on the Superconductivity of Ammonia‐Doped NaK2C60

Abstract

The role of structural effects on the anomalous superconducting properties of (NH₃) _x NaK₂C₆₀ fullerides was investigated using ²³Na and ²H NMR. In the metallic (NH₃) _x NaK₂C₆₀ (0.5 < x < 1) compounds, the ²³Na quadrupolar splitting is observed to be independent from ammonia concentration x which, on the other hand, substantially affects the superconducting transition temperature. The marginal influence of sodium cation displacement in the superconducting properties is confirmed also by the absence of any electric field gradients in the recently synthesized nonmagnetic insulator (NH₃)₂NaK₂C₆₀. ²H NMR measurements on deuterated samples enabled us to study the ND₃ reorientational dynamics, indicating a hampered ammonia rotation in the insulating (x = 2) case, where the Na⁺ ions become centered.     

Optimization of n nc-Si:H and a-SiNx:H layers for their application in nc-Si:H TFT

The n-type doped silicon thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) technique at high and low H₂ dilutions. High H₂ dilution resulted in n⁺ nanocrystalline silicon films (n⁺ nc-Si:H) with the lower resistivity (ρ ∼0.7 Ω cm) compared to that of doped amorphous silicon films (∼900 Ω cm) grown at low H₂ dilution. The change of the lateral ρ of n⁺ nc-Si:H films was measured by reducing the film thickness via gradual reactive ion etching. The ρ values rise below a critical film thickness, indicating the presence of the disordered and less conductive incubation layer. The 45 nm thick n⁺ nc-Si:H films were deposited in the nc-Si:H thin film transistor (TFT) at different RF powers, and the optimum RF power for the lowest resistivity (∼92 Ω cm) and incubation layer was determined. On the other hand, several deposition parameters of PECVD grown amorphous silicon nitride (a-SiN_x:H) thin films were changed to optimize low leakage current through the TFT gate dielectric. Increase in NH₃/SiH₄ gas flow ratio was found to improve the insulating property and to change the optical/structural characteristics of a-SiN_x:H film. Having lowest leakage currents, two a-SiN_x:H films with NH₃/SiH₄ ratios of ∼19 and ∼28 were used as a gate dielectric in nc-Si:H TFTs. The TFT deposited with the NH₃/SiH₄∼19 ratio showed higher device performance than the TFT containing a-SiN_x:H with the NH₃/SiH₄∼28 ratio. This was correlated with the N−H/Si−H bond concentration ratio optimized for the TFT application.     

CaSc2O4:Eu: A tunable full-color emitting phosphor for white light emitting diodes

We report an intense full-color emission originating from ⁵D_0,1,2,3 to ⁷F_0,1,2,3,4 transitions of Eu³⁺ in CaSc₂O₄ upon 395 nm excitation. The emission spectra vary with increasing Eu³⁺ concentration, demonstrating tunable color coordinates from white to red region in the CIE chromaticity diagram. Considering the relaxation from ⁵D_J to ⁵D_J−1 through cross energy transfer, the Eu³⁺ concentration dependent emission spectra are well simulated based on the analysis of steady state rate equations and the measured lifetimes of the ⁵D_J levels. It is suggested that CaSc₂O₄:Eu³⁺ could be a potential single-phased full-color emitting phosphor for near-ultraviolet InGaN chip pumped white light emitting diodes.     

A red-emitting heavy doped phosphor Li6Y(BO3)3:Eu for white light-emitting diodes

A series of Eu³⁺ activated Li₆Y_1−xEu_x(BO₃)₃ (0.05 ? x ? 1) phosphors were synthesized by solid-state reaction method. The structures and photoluminescent properties of the phosphors were investigated at room temperature. The results of XRD patterns indicate that these phosphors are isotypic to the monoclinic Li₆Gd(BO₃)₃. The excitation spectra indicate that these phosphors can be effectively excited by near UV (370-410 nm) light. The red emission from transition ⁵D₀→⁷F₂ is dominant. The emission spectra exhibit strong red performance (CIE chromaticity coordinates: x = 0.65, y = 0.35), which is due to the ⁵D₀−⁷F_J transitions of Eu³⁺ ions. The relationship between the structure and the photoluminescent properties of the phosphors was studied. The concentration quenching occurs at x ≈ 0.85 under near UV excitation. Li₆Y(BO₃)₃:Eu³⁺ has potential application as a phosphor for white light-emitting diodes.     

Er:YAl3(BO3)4 glassy thin films from polymeric precursor and sol-gel methods: Waveguides for integrated optics

This paper presents the characterization of single-mode waveguides for 980 and 1550 nm wavelengths. High quality planar waveguide structure was fabricated from Y_1 − xEr_xAl₃(BO₃)₄ multilayer thin films with x = 0.02, 0.05, 0.1, 0.3, and 0.5, prepared through the polymeric precursor and sol-gel methods using spin-coating. The propagation losses of the planar waveguides varying from 0.63 to 0.88 dB/cm were measured at 632.8 and 1550 nm. The photoluminescence spectra and radiative lifetimes of the Er^{3+ 4}I_13/2 energy level were measured in waveguiding geometry. For most samples the photoluminescence decay was single exponential with lifetimes in between 640 μs and 200 μs, depending on the erbium concentration and synthesis method. These results indicate that Er doped YAl₃(BO₃)₄ compounds are promising for low loss waveguides.     

151Eu Mössbauer studies on Zn-doped EuBa2Cu3O7−y

¹⁵¹Eu Mössbauer studies have been performed on the compounds EuBa₂(Cu_1?x Zn _x )₃O_7?y withx=0·0, 0·025, 0·05, 0·075 and 0·1. The parent compound, EuBa₂Cu₃O_7?y is superconducting with a transition temperature (T _c ) of 88 K.T _c is depressed as Zn is substituted for Cu in this system and the compounds withx>0·05 do not show superconductivity down to 12 K.¹⁵¹Eu Mössbauer studies at 295 K show a single Mössbauer line in all the compounds (whether superconducting or not) with isomer shift value typical of Eu^{3 +} ion. Further, the isomer shift values are nearly independent ofx and the temperatures down to 10 K. These observations imply that the Cu-O network responsible for superconductivity is very weakly coupled to the Eu sublattice.     

Synthesis and electrochemical properties of Ti doped Li3 − xFe2 − xTix(PO4)3/C cathode materials

Li_3 − xFe_2 − xTi_x(PO₄)₃/C (x = 0-0.4) cathodes designed with Fe doped by Ti was studied. Both Li₃Fe₂(PO₄)₃/C (x = 0) and Li_2.8Fe_1.8Ti_0.2(PO₄)₃/C (x = 0.2) possess two plateau potentials of Fe³⁺/Fe²⁺ couple (around 2.8 V and 2.7 V vs. Li⁺/Li) upon discharge observed from galvanostatic charge/discharge and cyclic voltammetry. Li_2.8Fe_1.8Ti_0.2(PO₄)₃/C has higher reversibility and better capacity retention than that of the undoped Li₃Fe₂(PO₄)₃/C. A much higher specific capacity of 122.3 mAh/g was obtained at C/20 in the first cycle, approaching the theoretical capacity of 128 mAh/g, and a capacity of 100.1 mAh/g was held at C/2 after the 20th cycle.     

Monophase domain, fibers single crystals grown by the micro-pulling down technique and optical characterisation of LiGd1−xYbx(WO4)2

We have determined the single phase domain of LiGd_1−xYb_x(WO₄)₂. The lattices parameters decrease as a function of Yb³⁺ substitution in Gd³⁺ sites. Transparent LiGd_1−xYb_x(WO₄)₂ fibers single crystals were successfully grown by the micro-pulling down technique (μ-PD). The Yb³⁺-doped LiGd(WO₄)₂ fibers single crystals have been pulled under stationary stable growth conditions corresponding to flat crystallization interface with meniscus length equal to 120 μm. The fibers diameters varied from 0.5 to 1 mm depending on the capillary die diameter, pulling rate and the molten zone temperature. Fibers single crystals free of defects are observed for Ytterbium concentration in the melt up to 5 at%. Above this limit, inclusions and cracks appear and the optical quality of the fibers were deteriorated. The emission spectra of Yb³⁺-doped LiGd(WO₄)₂ were investigated.