Spectroscopy of optical centers of Eu<Superscript>3+</Superscript> ions in partially stabilized and stabilized zirconium crystals

The structure of the optical centers of Eu³⁺ ions in tetragonal (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 2.7–3.6; y = 0.1) and cubic (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 8–38; y = 0.1–0.5) crystals of solid solutions on the basis of zirconium dioxide is studied using the methods of optical and Raman-scattering spectroscopy. Characteristic optical centers of Eu³⁺ ions with different crystalline environments are revealed in the above compounds.     

Photodynamic processes in CaF<Subscript>2</Subscript> crystals activated by Ce<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions

The photochemical properties of CaF₂ crystals activated by Ce³⁺ and Yb³⁺ ions are studied. A model of the photodynamic processes induced by pumping UV or VUV radiation in active media is suggested and experimentally verified. This model explains both the presence of color centers of electronic and hole nature in crystals activated by cerium and the mechanism of suppressing of solarization processes after additional activation of the samples by Yb³⁺ ions. The cross sections of the processes of free-carrier capture by various ytterbium impurity centers are estimated. These impurity centers are established to be effective centers of recombination of free carriers of both signs.     

Structure and spectral-luminescence properties of yttrium-stabilized zirconia crystals activated with Tm<Superscript>3+</Superscript> ions

Yttrium-stabilized zirconia crystals (ZrO₂-13.8 mol % Y₂O₃-0.2 mol % Tm₂O₃ and ZrO₂-12 mol % Y₂O₃-2 mol % Tm₂O₃) have been grown by directed crystallization from a melt in a cold container using direct high-frequency melting. The crystals have been analyzed by X-ray diffraction. The spectral-luminescence properties have been studied, and the cross-relaxation efficiency for Tm³⁺ ions (³ H ₄ → ³ F ₄, ³ H ₆ → ³ F ₄) in these crystals has been estimated.     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

Intensities of hypersensitive transitions in garnet crystals doped with Er<Superscript>3+</Superscript> ions

We examine the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of yttrium-aluminum, scandium-containing, and gallium garnet crystals doped with Er³⁺ ions. A comparative analysis of the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of garnets with different contents of Al³⁺ and Sc³⁺ ions (Gd_2.4Er_0.5Sc_1.8Al_3.3O₁₂, Gd_2.4Er_0.5Sc_1.9Al_3.2O₁₂, Gd_2.4Er_0.5Sc_2.0Al_3.1O₁₂) is performed, as a result of which the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of these crystals are shown to have close values. We find that Ca₃(NbGa)₅O₁₂ crystals doped with Er³⁺ ions are characterized by highest values of the oscillator strengths for hypersensitive transitions and of the intensity parameter Ω₂ of Er³⁺ ions compared to the values of these quantities in the examined garnet crystals, which is determined by the fact that the symmetry of the local environment of Er³⁺ ions in these crystals is C ₁, C ₂, or C _2ν. We reveal that, as the concentration of Er³⁺ ions in these crystals increases from 1 to 39 at %, both the oscillator strength of the hypersensitive transition ⁴ I _15/2 → ² H _11/2 of Er³⁺ ions and their intensity parameter Ω₂ tend to decrease, which can be related to an increase in the relative fraction of Er³⁺ ions with higher symmetry of the local environment.     

Spectroscopic indications of the possible optical cooling effect in fluoride crystals activated by Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

The results of spectral kinetic studies of several fluoride crystals activated by Yb³⁺ and Tm³⁺ ions are presented, and their possible application as cooling elements of optical refrigerators is discussed. Optimum excitation conditions for the laser cooling effect in these crystals are found. The cooling efficiency is established to depend on the degree of order in the active medium.     

Charge-transfer bands in crystals of alkaline earth fluorides with Eu<Superscript>3+</Superscript> and Yb<Superscript>3 + 1</Superscript>

The absorption, luminescence, and excitation spectra of CaF₂, SrF₂, and BaF₂ crystals with EuF₃ or YbF₃ impurity have been investigated in the range 1–12 eV. In all cases, strong wide absorption bands (denoted as CT₁) were observed at energies below the 4f ⁿ -4f ^{n ? 1}5d absorption threshold of impurity ions. Weaker absorption bands (denoted as CT₂) with energies 1.5–2 eV lower than those of the CT₁ bands have been found in the spectra of CaF₂ and SrF₂ crystals with EuF₃ or YbF₃ impurities. The fine structure of the luminescence spectra of CaF₂ crystals with EuF₃ impurities has been investigated under excitation in the CT bands. Under excitation in the CT₁ band, several Eu centers were observed in the following luminescence spectra: C _4v , O _h , and R aggregates. Excitation in the CT₂ bands revealed luminescence of only C _4v defects.     

Comparative Investigation on Nanocrystal Structure and Luminescence Properties of Gadolinium Molybdates Codoped with Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>

This paper reports on the comparative investigation of nanocrystal structure and luminescence properties of Er³⁺/Yb³⁺-codoped gadolinium molybdate nanocrystals Gd₂(MoO₄)₃ and Gd₂MoO₆ synthesized by the Pechini method with citric acid and ethylene glycol. Their crystallization, structure transformation, and morphologies have been investigated by X-ray diffraction, thermogravimetric/differential scanning calorimetry, and transmission electron microscopy. It is noticed that Er³⁺/Yb³⁺-codoped monoclinic Gd₂(MoO₄)₃ nanocrystals have shown an intense upconversion through a sintering of the organic complex precursor at 600°C. Furthermore, it transforms to orthorhombic Gd₂(MoO₄)₃ when the precursor is sintered at 900°C. In counterpart of monoclinic Gd₂MoO₆, however, the monoclinic structure remains unchanged when the precursor is sintered at a temperature ranging from 600°C to 900°C. Intense visible emissions of Er³⁺ attributed to the transitions of ²H_11/2, ⁴S_3/2–⁴I_15/2 at 520 and 550 nm, and ⁴F_9/2–⁴I_15/2 at 650 nm have been observed upon an excitation with a UV source and a 980 nm laser diode, and the involved mechanisms have been explained. It is quite interesting to observe obvious differences both in the excitation and the upconversion emission spectra of Er³⁺/Yb³⁺-codoped Gd₂(MoO₄)₃ respectively with monoclinic and orthorhombic structure. The quadratic dependence of fluorescence on excitation laser power has confirmed that two-photons contribute to upconversion of the green–red emissions.     

Growth and spectral-luminescent study of SrMoO<Subscript>4</Subscript> crystals doped with Tm<Superscript>3+</Superscript> ions

SrMoO₄ crystals doped with Tm³⁺ ions have been produced from a melt using the Czochralski method; their spectral-luminescent characteristics have been studied, and laser radiation has been generated at the wavelength of 1.94 μm using laser-diode excitation. The high absorption section at the wavelength of 795 nm, the fairly high luminescence section, the long lifetime at the upper laser level ³F4 of 1.5 ms, and a wide luminescence band allow one to hope for developing efficient tunable Tm³⁺: SrMoO₄ crystal lasers with diode pumping in the range of 1.7–2.0 μm, which are capable of implementing SRS self-transformation of radiation into the middle IR band.     

The upconversion luminescence and magnetism in Yb<Superscript>3+</Superscript>/Ho<Superscript>3+</Superscript> co-doped LaF<Subscript>3</Subscript> nanocrystals for potential bimodal imaging

Biocompatible upconversion nanoparticles with multifunctional properties can serve as potential nanoprobes for multimodal imaging. Herein, we report an upconversion nanocrystal based on lanthanum fluoride which is developed to address the imaging modalities, upconversion luminescence imaging and magnetic resonance imaging (MRI). Lanthanide ions (Yb³⁺ and Ho³⁺) doped LaF₃ nanocrystals (LaF₃ Yb³⁺/Ho³⁺) are fabricated through a rapid microwave-assisted synthesis. The hexagonal phase LaF₃ nanocrystals exhibit nearly spherical morphology with average diameter of 9.8 nm. The inductively coupled plasma mass spectrometry (ICP-MS) analysis estimated the doping concentration of Yb³⁺ and Ho³⁺ as 3.99 and 0.41%, respectively. The nanocrystals show upconversion luminescence when irradiated with near-infrared (NIR) photons of wavelength 980 nm. The emission spectrum consists of bands centred at 542, 645 and 658 nm. The stronger green emission at 542 nm and the weak red emissions at 645 and 658 nm are assigned to ⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺, respectively. The pump power dependence of luminescence intensity confirmed the two-photon upconversion process. The nanocrystals exhibit paramagnetism due to the presence of lanthanide ion dopant Ho³⁺ and the magnetization is 19.81 emu/g at room temperature. The nanocrystals exhibit a longitudinal relaxivity (r ₁) of 0.12 s^?1 mM^?1 and transverse relaxivity (r ₂) of 28.18 s^?1 mM^?1, which makes the system suitable for developing T2 MRI contrast agents based on holmium. The LaF₃ Yb³⁺/Ho³⁺ nanocrystals are surface modified by PEGylation to improve biocompatibility and enhance further functionalisation. The PEGylated nanocrystals are found to be non-toxic up to 50 μg/mL for 48 h of incubation, which is confirmed by the MTT assay as well as morphological studies in HeLa cells. The upconversion luminescence and magnetism together with biocompatibility enables the adaptability of the present system as a nanoprobe for potential bimodal imaging.     

LiNbO<Subscript>3</Subscript>:Yb<Superscript>3+</Superscript> crystals for optical temperature sensors

Possibilities of using lithium niobate crystals, doped with ytterbium (LN:Yb³⁺) as materials for optical temperature sensor (OTS), are discussed. We consider both the radiative and absorptive characteristics of the crystals, assuming that their temperature dependences are caused by the Boltzmann factor of the initial population of Stark sublevels of the ion. It is shown that the crystals can be used as materials for OTS in the temperature range 150–400 K.     

CW and tunable laser operation of Yb<Superscript>3+</Superscript> doped CaF<Subscript>2</Subscript>

We present the spectroscopic properties and room temperature of a cw tunable laser operation with Yb³⁺ doped CaF₂ single crystals grown in our laboratory. A laser slope efficiency of 50% with respect to the absorbed 920 nm pump power was obtained, and the laser wavelength could be tuned between 1000 and 1060 nm. PACS 42.55R; 42.70An erratum to this article can be found at     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

Defect Structure and Up-conversion Luminescence Properties of ZrO<Subscript>2</Subscript>:Yb<Superscript>3+</Superscript>,Er<Superscript>3+</Superscript> Nanomaterials

The up-converting ZrO₂:Yb³⁺,Er³⁺ nanomaterials were prepared with the combustion and sol–gel methods. FT-IR spectroscopy was used for analyzing the impurities. The crystal structures were characterized with X-ray powder diffraction and the mean crystallite sizes were estimated with the Scherrer formula. Up-conversion luminescence measurements were made at room temperature with IR-laser excitation at 977 nm. The IR spectra revealed the conventional and OH⁻ impurities for the combustion synthesis products. The structure of the ZrO₂:Yb³⁺, Er³⁺ nanomaterials was cubic except for the minor monoclinic and tetragonal impurities obtained with the sol–gel method. The materials showed red (650–700 nm) and green (520–560 nm) up-conversion luminescence due to the ⁴F_9/2→⁴I_15/2 and (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺, respectively. The products obtained with the combustion synthesis exhibited the most intense luminescence intensity and showed considerable afterglow.     

Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

Wavelength tunable femtosecond laser based on short Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> codoped phosphate fiber

A wavelength tunable laser system mode-locked by nonlinear polarization evolution based on a 3 cm-long homemade Er³⁺/Yb³⁺ codoped phosphate fiber has been reported. By simply adjusting the polarization controllers, the central wavelength of the mode-locked spectrum can be tuned over 1537.1–1563.3 nm continuously. Moreover, 264-fs pulse with 3-dB spectral width of 39.6 nm and peak power of 7.8 kW at a 7.55 MHz repetition rate is generated directly from the all-fiber ring cavity.     

Interaction of <Superscript>3</Superscript>He<Superscript>2+</Superscript> and Ar<Superscript>6+</Superscript> ions with acetylene,ethylene, and ethane molecules

Time-of-flight mass spectroscopy methods are employed for studying processes occurring during capture of electrons by ³He²⁺ and Ar⁶⁺ multiply charged ions with energy 6z keV (z is the ion charge) from C₂H _n molecules (n = 2, 4, 6) with different multiplicities of C-C bonds. Fragmentation schemes of the molecular ions formed in such processes are established from analysis of correlations of recording times for all fragment ions. The absolute values of the cross sections of capture of an electron and capture with ionization are measured, as well as the cross sections of formation of fragment ions in these processes. The absolute values of total capture cross sections for several electrons are determined.     

30-W Yb<Superscript>3+</Superscript>-pulsed fiber laser with wavelength tuning

We have investigated various pulsed operation regimes of a diode-pumped Yb³⁺-doped fiber laser with both an acoustooptic filter and a shutter inside the resonator. To imbed the polarization-sensitive acoustooptic-tunable spectral filter into the polarization-nonmaintaining resonator, based on an “isotropic” single-mode fiber without “polarization’ losses, we have used a CaCO₃ single-crystal nondispersive thermostable polarization splitter. Stable smooth bell-shaped laser pulses were obtained in the Q-switch generation regime across the entire wavelength tuning band. Their duration depended on the resonator travel time and their repetition rate was determined exclusively by the outer high-frequency generator controlling the acoustooptic shutter. A pulsed laser radiation tuning bandwidth of more than 20-nm at a repetition rate band of 10–100 kHz was observed in the amplification band of the Yb³⁺-doped fiber. A stable average power of 30 W of the pulsed 70-ns 100-kHz laser radiation in a near Gaussian beam was reached by means of the two-stage amplifier based on Yb³⁺-doped fibers with an enlarged mode field diameter (14 μm). The amplifier was pumped by λ = 975 nm CW multimode laser diodes with a maximum average power of 42 W.