Facile synthesis and luminescence properties of uniform and monodisperse KY3F10:Ln3+ (Ln=Eu,Ce, Tb) nanospheres

Highly uniform and monodisperse KY₃F₁₀:Ln³⁺ (Ln=Eu, Ce, Tb) nanospheres, with an average diameter of 300 nm, have been successfully prepared through a simple template-free and surfactant-free stirring method under ambient conditions. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectra were used to characterize the samples. The SEM images illustrate that these spheres were actually composed of randomly aggregated nanoparticles. The doped rare earth ions show their characteristic emission in the KY₃F₁₀ samples, i.e., Eu^{3+ 5}D₀–⁷F_J (J=1, 2, 3, 4), Tb^{3+ 5}D₄–⁷F_J (J=6, 5, 4, 3, 2) and Ce³⁺ 5d–4f transition emissions, respectively. An energy transfer phenomenon from Ce³⁺ to Tb³⁺ has been observed in KY₃F₁₀ nanospheres, and the energy transfer efficiency depends on the doping concentration of Tb³⁺ if the concentration of Ce³⁺ is fixed.     

Effect of Ce co-doping on KY3F10:Pr crystals

A spectroscopic investigation on the effect of Ce³⁺ co-doping in fluoride KY₃F₁₀:Pr³⁺ crystals is presented. In particular spectroscopic measurements of three different samples of KY₃F₁₀ crystal doped with 0.3at% Pr³⁺ and co-doped with 0at%, 0.17at% and 0.3at% Ce³⁺ are discussed. Details on the growth of the crystals are also reported. Measurements were performed in the temperature range 10-300 K. Fluorescence and lifetime measurements have shown a cross relaxation between ³P₀-¹D₂ levels of Pr³⁺ and ²F_7/2-²F_5/2 of Ce³⁺. Data exhibit that this effect is strictly related to the Cerium concentration.     

The pH-dependent reactions in the sonochemical synthesis of luminescent fluorides: The quest for the formation of KY3F10 crystal phases

In this study Eu³⁺-doped yttrium fluorides were designed by ultrasound-assisted processes at different pH values (4.0–9.0). This novel strategy has enabled to obtain materials with intriguing morphologies and modulated crystal structures: α-KY₃F₁₀, δ–KY₃F₁₀·xH₂O, and Y(OH)_3–xF_x. To date, the literature has primarily focused only on the α-phase of KY₃F₁₀. Yet, explaining the formation of the mostly uncharted δ-phase of KY₃F₁₀ remains a challenge. Thus, this paper offers the key to synthesizing both the α and the δ-phases of KY₃F₁₀ and also reports the first ultrasound-assisted process for the preparation of yttrium hydroxyfluorides. It is also unraveled the connection between the different pH-dependent reactions and the formation mechanisms of the compounds. In addition to this, the unique features of the Eu³⁺ ion have allowed to conduct a thorough study of the different materials and have endowed the compounds with photoluminescent properties. The results underscore a highly tunable optical response, with a wide gamut of color emissions (from orangish to red hues), lifetimes (from 7.9 ms to 1.1 ms) and quantum efficiencies (98–28%). The study unveils the importance of sonochemistry in obtaining luminescent fluorides with controlled crystal structures that can open up new avenues in the synthesis and design of inorganic materials.     

Investigation of gain characteristics in mixed crystals LiMeF4 (Me = Y,Lu, Yb) doped by Ce3+ ions

Differential gain spectra in the range 295–335 nm were measured in crystals of scheelite structure LiY_{1 ? x} Lu _x F₄ (x = 0–1), doped by Ce³⁺ ions. It is shown that variation of Lu³⁺ and Y³⁺ ions relative content in LiY_{1 ? x} Lu _x F₄ crystals allows to manipulate the spectral width of the amplification band. Cross-sections of excited-state absorption at the wavelengths of Ce³⁺ luminescence, probability ratios of formation and thermal destruction of color centers depending on the Y³⁺ ions content in LiY_{1 ? x} Lu _x F₄ crystals were estimated. Even better gain characteristics have been demonstrated by LiLuF₄:Ce³⁺, doped by Yb³⁺ ions. The highest optical gain coefficient with a wide amplification band among studied samples was observed in LiLuF₄:Ce³⁺ crystal, codoped by Yb³⁺ ions.     

Ionization of helium-like ions with excitation of nl states by high-energy photon scattering

The kinetic and spectral characteristics of the complex dielectric constant of a Ce: YAG crystal under laser irradiation in 250–275 nm spectral range are investigated. The lifetimes of free charge carriers and charge carriers, localized at the lattice defects (color centers), are estimated. It was established that photoconductivity signal of the sample is essentially caused by one-photon ionization processes from the ² F _5/2 ground state of Ce³⁺ ions.     

The laser-diode-excited 5d-4f luminescence of Ce3+ and Pr3+ ions embedded into a BaR2F8 matrix

We show the possibility of obtaining UV luminescence from 5d-4f transitions of rare-earth ions in the BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) crystal under upconversion excitation by standard laser diodes with lasing wavelengths of 960, 808, and 840 nm. Various upconversion mechanisms of pumping for populating the higher-lying energy levels of the active ions, as well as methods of adaptation of the active medium BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) to these mechanisms, are considered.     

Formation of a stable bivalent state of Yb ions in Na4Y6F22:Ce3+, Yb3+ crystal under intense UV irradiation

The evolution dynamics of absorption spectra induced in samples of Na₄Y₆F₂₂:Ce³⁺, Yb³⁺ crystal by radiation resonant with 4f-5d transitions of Ce³⁺ ions was studied and analyzed. It was found that at least two types of color centers with different life times are induced in the studied crystal. It is established that the group of absorption bands in the UV spectral range that demonstrate long-term stability after excitation is caused by the 4f ¹³–4f ¹²5d transitions of bivalent ytterbium ions. The sequence of processes that lead to the reduction of ytterbium ions from the trivalent to the bivalent state is proposed.     

Electron paramagnetic resonance in mixed crystals (BaF<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript> activated by Ce<Superscript>3+</Superscript> ions

The electron paramagnetic resonance (EPR) spectra of mixed crystals (BaF₂)_{1?x? y}(LaF₃)_x(CeF₃)_y (y = 0.001 = 0.1%, x = 0–0.02) are investigated in a magnetic field H‖C₄ at a frequency of 9.5 GHz. The angular dependence of the EPR spectrum is measured for the sample with x = 0.02. The lines attributed to Ce³⁺ impurity centers with tetragonal symmetry and g factors (g_‖ = 0.75, g_⊥ = 2.4) close to those measured for the KY₃F₁₀: Ce³⁺ compound are separated in the complex EPR spectrum. The assumption is made that the aforementioned impurity centers are cubooctahedral clusters of the La₆F₃₇ type in which one of the La³⁺ ions is replaced by the Ce³⁺ ion.     

The radiation induced color centers of the LaBr3:Ce crystal

This paper presents study of the gamma-rays induced radiation damage in the LaBr₃:Ce crystal. The light output and transmittance are measured before and after γ-rays irradiations with an integrated dose up to 10⁶ rad for two LaBr₃:Ce samples. After γ-rays irradiation, LaBr₃:Ce crystal shows very slow recovery process or has no recover under room temperature, indicating that the radiation damage in LaBr₃:Ce crystal is not dose date dependent. Meanwhile, it's found that the radiation induced color centers are respectively peaked at the wavelength of 448 nm, 512 nm and 590 nm. Those color centers should be ascribed to the V_k, V_F and F center respectively.     

New all-solid-state tunable UV Ce3+, Yb3+:LiY0.4Lu0.6F4 laser

Here we report laser test results of the new UV solid-state active medium based on a Ce³⁺, Yb³⁺:LiY_0.4Lu_0.6F₄ mixed crystal pumped by radiation from Ce:LiCAF laser. The 10-Hz pulse repetition rate Ce³⁺, Yb³⁺:LiY_0.4Lu_0.6F₄ laser yielded a maximum output power of 0.25 mJ at 311nm in non-optimized non-selective resonator with a maximal slope efficiency of 13%. Tunability from 304 to 332 nm was achieved in the selective single-prism resonator.     

Optical and gain properties of series of crystals LiF-YF3-LuF3 doped with Ce and Yb ions

Here, we present first results of systematic studies of host cation variation impact on spectral-kinetic, photochemical and gain properties of Ce³⁺-doped LiYF₄ (YLF), LiLuF₄ (LLF) and LiY_1−xLu_xF₄ family crystals. 5d-4f luminescence decay of Ce³⁺ ions studies, together with pump-probe experiments, indicate that previously reported twice higher luminescence quantum yield in LLF compared with that of YLF crystals is provided by more efficient upper lasing level feeding due to recombination and higher color center destruction rate in LLF against YLF crystals. Namely, it is responsible for higher energetic characteristics of laser based on Ce³⁺:LLF crystals. Strong and wide pump-induced absorption band centered at 310 nm is observed in Ce³⁺:YLF. This band is shifted to blue and its intensity goes down with Lu content. We have evaluated free charges recombination rate, excited state absorption cross-section for Ce³⁺ ions and some other photodynamic processes related microparameters. Fitting results indicate that pump-induced color centers lifetime decreases with Lu-content in LiYF₄-LiLuF₄ mixture and it can be associated with more efficient color center bleaching by Ce³⁺ ions 5d-4f fluorescence.     

White LED based on nano-YAG:Ce3+/YAG:Ce3+,Gd3+ hybrid phosphors

Nano-YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ phosphors were synthesized by glycothermal method. The X-ray diffraction (XRD) measurements showed that the samples can be well-crystallized at 600 °C. The transition electron microscope (TEM) showed that the particles have sizes mostly in the range between 35 and 100 nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow peaking at 532 nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 nm to 568 nm has been achieved as doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White LEDs were fabricated by combining GaN (460 nm) chip with the YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺. Color rendering index of the white LED as a function of the ratios of theses two kinds of phosphors was studied. As the ratio of YAG:Ce³⁺,Gd³⁺ phosphor increased, the color rendering index of the LED improved significantly under the forward bias of 20 mA. As the ratio of YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ was 11:9, the white LED had a color rendering index, CIE chromaticity coordinates and color temperature T_c of 85, (0.3116, 0.3202) and 6564 K, respectively.     

Low-temperature high-resolution VUV spectroscopy of Ce doped LiYF4, LiLuF4 and LuF3 crystals

For LiYF₄:Ce³⁺, LiLuF₄:Ce³⁺ and LuF₃:Ce³⁺ crystals UV/visible emission and time-resolved VUV/UV excitation spectra were recorded at liquid helium temperature with spectral resolution of 0.1 nm for excitation spectra and better than 0.3 nm for emission spectra. Well resolved fine structures due to zero-phonon lines were clearly observed in both excitation and emission spectra for LiYF₄:Ce³⁺ and LiLuF₄:Ce³⁺. For LuF₃:Ce³⁺ crystal no fine structure was detected in the spectra even at the highest spectral resolution. Under the host excitation, the fine structure for high-energy emission band of Ce³⁺ (5d-²F_5/2) in LiLuF₄:Ce³⁺ becomes well pronounced because of weaker reabsorption effect, as compared to Ce³⁺ 4f-5d absorption, due to small penetration depth for exciting radiation. As a result the crystal-field splitting for ²F_7/2 and ²F_5/2 levels of Ce³⁺ in LiLuF₄ crystal was measured. First observation of zero-phonon lines at ∼81,550 and ∼82,900 cm⁻¹ as well as vibronic side bands due to interconfigurational 4f¹⁴-4f¹³5d transitions in Lu³⁺ is reported for excitation spectrum of LiLuF₄:Ce³⁺.     

Luminescence of LaBr3: Ce,Hf crystals under photon excitation in the ultraviolet,vacuum ultraviolet,and X-ray ranges

This study has been carried out using synchrotron radiation, time-resolved luminescence ultraviolet and vacuum ultraviolet spectroscopy, optical absorption spectroscopy, and thermal activation spectroscopy. It has been found that, in scintillation spectrometric crystals LaBr₃: Ce,Hf characterized by a low hygroscopicity, along with Ce³⁺ centers in regular lattice sites, there are Ce³⁺ centers located in the vicinity of the defects of the crystal structure. It has also been found that the studied crystals exhibit photoluminescence (PL) of new point defects responsible for a broad band at wavelengths of 500–600 nm in the PL spectra. The minimum energy of interband transitions in LaBr₃ is estimated as E _g ～ 6.2 eV. The effect of multiplication of electronic excitations has been observed in the range of PL excitation energies higher than 13 eV (more than 2E _g ). Thermal activation studies have revealed channels of electronic excitation energy transfer to Ce³⁺ impurity centers.     

Photoconductivity and photodielectric effect in LiY1 − x Lu x F4 crystals doped with Ce3+ and Yb3+ ions

Time and spectral dependences of the dielectric permittivity of the LiY_{1 ? x} Lu _x F₄ (x = 0, 0.5, and 1) crystals doped with Ce³⁺ and co-doped with Yb³⁺ ions under UV laser excitation were studied by the 8-mm microwave resonant technique at room temperature. The obtained photoconductivity spectrum in 240–310 nm spectral range was interpreted as a stepwise photoionization spectrum of the Ce³⁺ ions due to sequential 4f–5d and 5d–6s transitions. Average lifetimes of free and defect trapped (color centers) charge carriers were estimated.     

Electron paramagnetic resonance of Ce3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Ce³⁺ impurity ions in single crystals of lead thiogallate PbGa₂S₄ have been reported. The Ce³⁺ ions substitute for Pb²⁺ ions in the crystal lattice of PbGa₂S₄. A number of paramagnetic cerium centers in lead thiogallate have been observed. The spectra are described by the spin Hamiltonian of rhombic symmetry with the effective spin S = 1/2. The g factors of the main cerium centers have been determined. A large number of paramagnetic centers are due to both nonequivalent positions of lead and local charge compensation under the substitution Ce³⁺ ?? Pb²⁺.     

Luminescence and radiation-induced color centers in anion-defective alumina crystals after high-dose irradiation

A method of UV spectroscopy was used to measure photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra in anion-defective alumina crystals exposed to high doses of gamma-radiation. An additional emission band in the range of 1.6–2.75 eV appears in the exposed crystals. Aggregate F₂-type centers in different charge states are responsible for this band. It was found that growing intensity of PL aggregate centers occurs at doses corresponding to saturation of dose response and is accompanied by a sharp drop in the intensity of F⁺-band in the PL spectrum resulting from combination of F⁺-centers into aggregates. Uncharged F₂-centers are formed when electrons are trapped by F₂⁺ and F₂²⁺-centers. The main role of F⁺-centers in radiation-induced transformations of color centers under high-dose irradiation of anion-defective alumina crystals was indicated.     

Influence of J-mixing on the phenomenological interpretation of the Eu3+ ion spectroscopic properties

Two sets of B^k_q crystal field parameters and Bγ_kq intensity parameters have been calculated from the transition occuring between the Stark levels of Eu³⁺ in KY₃F₁₀. One of the calculations includes the J-mixing; the other not. The influence of the J-mixing on the intensities of the “forbidden” transition ⁵D₀ → ⁷F₀ and on the hypersensitive transitions are analysed.     

Photoluminescence properties of rare earth doped α-Si3N4

The photoluminescence properties of Eu²⁺, Ce³⁺ and Tb³⁺ doped α-Si₃N₄ have been studied and a possible structural model has been proposed on the basis of the Rietveld refinement of X-ray powder diffraction data. Nearly single phase rare earth doped α-Si₃N₄ was synthesized by a solid state reaction at 1600 °C in N₂-H₂ atmosphere starting from amorphous Si₃N₄ and rare earth oxides or nitrides. Because of small crystal field splitting of the 5d levels, the excitation and emission bands of Eu²⁺ and Ce³⁺ are positioned at higher energies as isolated ions in comparison with that in Ca-α-Sialon. Both Eu²⁺- and Ce³⁺-doped α-Si₃N₄ show blue band emission peaking at about 470 and 450 nm, respectively, under UV excitation. α-Si₃N₄:Tb³⁺ exhibits dominant green line emission mainly arising from ⁵D₄→⁷F_J (J=6-3) with weak ⁵D₃→⁷F_J (J=6-3) transitions of Tb³⁺ when excited by UV light. The thermal stability of α-Si₃N₄:Eu²⁺ is comparable with that of Ca-α-Sialon:Eu²⁺ and is much better than that of α-Si₃N₄:Ce³⁺.