Crystal Growth and Spectroscopic Characterisation of BiB3O6:RE3+ (RE3+ = Pr3+, Nd3+, Gd3+, Er3+, Tm3+)

Large single crystals of optical quality of BiB₃O₆:RE³⁺ (RE³⁺ = Pr³⁺, Nd³⁺, Gd³⁺, Er³⁺, Tm³⁺) were grown from nearly stoichiometric melts using the top‐seeding growth technique to dimensions up to 12 x 12 x 18 mm³. Absorption spectra were measured in the wavelength range from 10000 cm^‐1 to 30000 cm^‐1 with an absorption spectrometer to estimate the doping concentration of RE³⁺. For the determination of the phonon energies and the quenching behaviour of the host lattice IR and Raman spectra were recorded.     

Photoacoustic Spectra of Pr3+, Nd3+, Gd3+ Acetate Complexes

The crystals of the complexes Pr(Ac)₃ · 4 H₂O, Nd(Ac)₃ · 4 H₂O, Gd(Ac)₃ · 4 H₂O were synthesized and their Pa spectra determined firstly. Their PA spectra and absorption are interpreted. The fluorescence properties of Pr³⁺, Nd³⁺, Gd³⁺ and the relaxation process models were studied by their PA spectra.     

In situ chemical co-precipitation synthesis of YVO4:RE (RE = Dy3+, Sm3+, Er3+) phosphors by assembling hybrid precursors

YVO₄:RE (RE = Dy³⁺, Sm³⁺, Er³⁺) were prepared via an in situ chemical co-precipitation technology, and the assembly process of hybrid precursors was as follows: using rare earth coordination polymers with salicylic acid as precursors and composing with the polyvinyl alcohol (PVA) as dispersing media. Their microstructure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM), which indicate that there exist some novel cobblestone-like microcrystalline particles. All the doped rare earth ions showed their characteristic emissions in YVO₄ hosts. The concentration quenching all appeared of the three dopant ions and the optimum concentrations for Dy³⁺, Er³⁺, Sm³⁺ were determined to be 2, 3, 1 mol% in yttrium vanadate particles, respectively.     

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd³⁺, Mn²⁺ and Cu²⁺ heat treated at different temperatures, ranging from the glass transition temperature (T_g) to the crystallization temperature (T_c), are investigated by electron paramagnetic resonance (EPR) and ¹⁹F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu²⁺ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba₂ZnF₆, which correspond to Cu²⁺ in a tetragonal compressed F⁻ octahedron and to Cu²⁺ on interstitial sites with a square-planar F⁻ co-ordination. The EPR spectra of the Mn²⁺ doped glasses exhibit a sextet structure due to the Mn²⁺ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn²⁺ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn²⁺ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn²⁺ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd³⁺ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd³⁺ ions in environment close to cubic symmetry. The ¹⁹F NMR spin–lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above T_c. For the glass samples (doped or undoped) the ¹⁹F magnetization recoveries were found to be adjusted by an exponential function and the spin–lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above T_c, the ¹⁹F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu²⁺, Mn²⁺, Gd³⁺ EPR spectra and NMR relaxation, are always observed for the samples annealed above T_c.     

Photoluminescence of Sm3+, Dy3+, and Tm3+-doped transparent glass ceramics containing CaF2 nanocrystals

Photoluminescence properties of Sm³⁺, Dy³⁺, and Tm³⁺-doped transparent oxyfluoride silicate glass ceramics containing CaF₂ nanocrystals were reported. Emission bands of ⁴G_5/2 → ⁶H_5/2 (562 nm), ⁴G_5/2 → ⁶H_7/2 (598 nm), ⁴G_5/2 → ⁶H_9/2 (645 nm) and ⁴G_5/2 → ⁶H_11/2 (706 nm) for the Sm³⁺: glass and glass ceramic, with an excitation at ⁶H_5/2 → ⁴F_7/2 (402 nm) have been recorded. Of them, ⁴G_5/2 → ⁶H_7/2 (598 nm) has shown a bright orange emission. With regard to the Dy³⁺: glass, a bright fluorescent yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) and blue emission at 481 nm (⁴F_9/2 → ⁶H_15/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 386 nm (⁶H_15/2 → ⁴I_13/2 + ⁴F_7/2) wavelength. Emission bands of ¹G₄ → ³F₄ (650 nm) and ¹G₄ → ³H₅ (795 nm) transitions for the Tm³⁺: glass and glass ceramic, with an excitation at ³H₆ → ¹G₄ (467 nm) have been observed. Of them, ¹G₄ → ³F₄ (650 nm) has shown bright red emission. Decay lifetime measurements were also carried out for all the observed Sm³⁺, Dy³⁺, and Tm³⁺-doped glass and glass ceramic emission bands.     

Chemical co-precipitation synthesis of luminescent BixY1−xVO4: RE (RE = Eu3+, Dy3+, Er3+) phosphors from hybrid precursors

Using novel synthesis technology, novel luminescent materials of Bi_zY_0.95−xEu_0.05VO₄, Bi_xY_0.97−zDy_0.03VO₄ and Bi_xY_0.98−xEr_0.02VO₄ were prepared. An in situ co-precipitation technology was used to assemble the hybrid precursors. Rare earth coordination polymers with aromatic carboxylic acids were used as the precursors of rare earth oxide components, and polyethylene glycol (PEG) and ammonium vanadate (NH₄VO₃) were composed to assemble inorganic/organic hybrid polymeric dispersing media. Their microstructure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and scanning electronic microscope (SEM). All the emission spectra showed the characteristic absorption of Eu³⁺, Dy³⁺ and Er³⁺, respectively, in the host of YVO₄–BiVO₄.     

Single‐crystal growth and characterization of mullite‐type orthorhombic Bi2M4O9 (M = Al3+, Ga3+, Fe3+)

Pure and homogeneous single crystals of orthorhombic mullite‐type Bi₂M₄O₉ (M = Al³⁺, Ga³⁺, Fe³⁺), and a mixed Bi₂Fe_1.7Ga_2.3O₉ crystal from an equimolar Ga/Fe composition were grown by the top seeded solution growth (TSSG) method. All these compounds melt incongruently in the range of about 800 and 1100 °C. In case of bismuth gallate and ferrate inclusion‐free crystals with dimensions up to several cubic centimeters can be grown. Limited solubility in Bi₂O₃ and the high steepness of the liquidus curve are the reasons for getting only small imperfect bismuth aluminate crystals. In contrast to ceramic materials preparation reported in literature, divalent calcium and strontium could not be incorporated into the mullite‐type structure during the melt growth process. Several fundamental physical properties like heat capacity, thermal expansion, heat conductivity, elastic constants, high‐pressure behavior and oxygen diffusivity were determined by different research groups using single‐crystalline samples from the as‐grown materials. Furthermore, the refractive indices of Bi₂Ga₄O₉ were measured in the range of 0.430 and 0.700 μm. Such as many other bismuth containing compounds the refractive indices of Bi₂Ga₄O₉ are larger than 2, and Bi₂Ga₄O₉ is an optic biaxial positive crystal. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication of Cr4+,Nd3+:YAG transparent ceramics for self-Q-switched laser

Transparent 0.1 at.%Cr,1.0 at.%Nd:YAG (Y₃Al₅O₁₂) ceramics were fabricated by a solid-state reaction and vacuum sintering with CaO as a charge compensator and tetraethyl orthosilicate (TEOS) as a sintering aid using high-purity powders of Al₂O₃, Y₂O₃, Nd₂O₃ and Cr₂O₃. The mixed powder compacts were sintered at 1800 °C for 5 h and 30 h under vacuum. The optical transmittance of the Cr,Nd:YAG ceramics sintered at 1800 °C for 5 h and 30 h is ∼63% and ∼78% in the infrared wavelengths, respectively. The two samples exhibit pore-free structures and the average grain size is about 10 and 20 μm. For the sample sintered at 1800 °C for 5 h, the dominant fracture mechanism is the transgranular fracture. With increase of holding time up to 30 h, the ratio of intergranular fracture surfaces increase and more Cr³⁺ ions in the Cr,Nd:YAG ceramic transform to Cr⁴⁺. High-quality Cr⁴⁺,Nd³⁺:YAG transparent ceramics may be a potential self-Q-switched laser material.     

H2O influence evaluating and mid-IR fluorescence quenching in Tm3+-doped GeGaSCsI chalcohalide glasses

This work presents a detailed study on near-infrared and mid-infrared fluorescence emissions with five sets of Tm³⁺-doped 75GeS₂–15Ga₂S₃–10CsI chalcohalide glass. They are prepared in normal or water drying process. Based on the diffusion-limited relaxation calculation, a detailed investigation is put forward to obtain efficient near-infrared or mid-infrared fluorescence emissions of Tm³⁺ on the effect of H₂O on the Tm³⁺ fluorescence. Detailed investigations are given to the interacted energy transferring processes between rare-earth, impurities and vibrating phonons with the appearance of fluorescence quenching, along with Tm³⁺, H₂O concentrations varying and energy gaps forming. The radioactive properties are analyzed using compensated diffusion-limited relaxation calculation method, and the near-IR and mid-IR fluorescence properties are evaluated in detail with experimental and theoretical analysis.     

Growth and Optical Properties of Doped LiTaO3 Single Crystals

Single crystals of lithium tantalate (LiTaO₃) doped with Pr, Nd + Yb and Tm were grown by the Czochralski method. A thermal system with 50 mm diameter iridium crucible and two different afterheaters (active and passive) was checked with respect to temperature distribution in a pulling region. The obtained crystals were up to 20 mm in diameter and up 50 mm in length. Crystals were poled, and the Curie temperature was determined for specimens cut of from different parts of single crystals. The polarized absorption spectra, time resolved emission spectra and emission lifetime of Pr³⁺ doped LiTaO₃ crystals were measured. An intense emission from the ³P₀ level was observed. Optical properties of the Yb³⁺ ions excited by energy transfer from Nd3+ ions have been researched for LiTaO₃:Nd, Yb crystals.     

Synthesis and structure of two crystalline modifications of Bis(1,10-Phenanthroline)trinitratoeuropium(III) Eu(NO3)3(Phen)2

Two crystalline modifications (I and II) of the phenanthroline complex of europium nitrate with the same chemical composition, Eu(NO₃)₃(Phen)₂, are synthesized under different conditions by varying the solvents, temperatures, and crystallization rates. The crystal structures of these modifications are determined using X-ray diffraction. Crystalline modifications I and II differ in the unit cell parameters and the positions of the complexes in the unit cell. The geometric characteristics of the complexes in the structures of compounds I and II differ insignificantly. Crystals of compound I belong to the isostructural family Ln(NO₃)₃(Phen)₂ (Ln = La-Lu). Crystals of compound II (new phase) are studied for the first time. Crystals of I and II are monoclinic, space group C2/c, and Z = 4. The unit cell parameters are as follows: a = 11.1555(10) Å, b = 17.9698(10) Å, c = 13.0569(10) Å, β = 100.507(10)°, and V = 2572.1(3) ų for modification I and a = 9.5153(10) Å, b = 15.4546(10) Å, c = 17.1763(10) Å, β = 93.451(10)°, and V = 2521.3(3) ų for modification II. The difference between the molecular complexes in the structures of compounds I and II is revealed by the superposition method. Complexes II are arranged along the C ₂ axis and are statistically disordered with respect to this axis.     

New transition metal fluoride glasses isolated in the PbF2MtIIF2MtIIIF3 systems

New glasses have been prepared in the PbF₂M_t^IIF₂M_t^IIIF₃ systems (m_t^II = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺; M_t^III = Fe³⁺, V³⁺, Cr³⁺, Ga³⁺). The extent of the vitreous area is shown in a PbF₂MnF₂FeF₃ diagram. Thermal properties have been measured for all samples. Some of these glasses are very transparent over a wide range of wavelengths (from 250–12 000 nm). The sixfold coordination of transition metal ions has been established by spectroscopic investigations. The structure of the glasses is discussed on the basis of a random corner-sharing of MF₆ octahedra.     

Synthesis and the crystal and molecular structure of two modifications of bis(1,10-phenanthroline)trinitratoerbium(III) Er(NO3)3(Phen)2

Two crystalline modifications (I and II) of the phenanthroline complex of erbium nitrate with the same chemical composition, Er(NO₃)₃(Phen)₂, are synthesized by a procedure similar to that used for preparing the phenanthroline complexes of europium nitrate. The crystal structures of these modifications are determined using X-ray diffraction. Crystals of compound I belong to the isostructural family Ln(NO₃)₃(Phen)₂ (Ln = La-Lu). Crystals of compound II are isostructural to those of modification II (new phase) of the Eu(NO₃)₃(Phen)₂ compound. Crystals of I and II are monoclinic, space group C2/c, and Z = 4. The unit cell parameters are as follows: a = 11.126 Å, b = 17.815 Å, c = 12.976 Å, β = 100.45°, and V = 2529 ų for modification I and a = 9.459 Å, b = 15.463 Å, c = 17.076 Å, β = 93.52°, and V = 2493 ų for modification II. The molecular complexes in the structures of compounds I and II are nearly identical. The mean lengths of the Er-N and Er-O bonds are equal to 2.500 and 2.466 Å in compound I and 2.508 and 2.457 Å in compound II, respectively. The difference between the structures of compounds I and II is associated with the difference between intermolecular interactions in the unit cell.     

Development of LuAG-based scintillator crystals – A review

A review of research and development of Lu₃Al₅O₁₂ (LuAG)-based single crystal scintillators is presented. Crystals of this type have been prepared by the micro-pulling down method at the initial stage of material screening and by Czochralski or Bridgman methods to obtain higher quality and larger size single crystals afterward. Several different activators, namely Ce³⁺, Pr³⁺, Yb³⁺ and Sc³⁺ have been reported in the literature and such doped LuAG single crystals have been extensively studied to understand a number of issues, including: the scintillation mechanism, underlying energy transfer and trapping processes including the nature and role of material defects involved in the scintillation process and their relation to manufacturing technology. Significant improvements in the understanding of aluminum garnet scintillators lead to the discovery of multicomponent garnet single crystal scintillators in 2011, which are described. These materials gave rise to new class of ultraefficient complex oxide scintillators, the light yield of which considerably exceeds the values achieved for the best Ce-doped orthosilicate scintillators.     

Crystal structure of calcium trans-N-(nitrilotriacetato)(pyridine-2-carboxylato)cobaltate(III) hexahydrate, Ca[Co(Nta)(Pic)]2] · 6H2O

Crystals of Ca[Co^III (Nta)(Pic)]₂ · 6H₂O (I) (where Nta ^3? and Pic ^? are the nitrilotriacetate and picolinate ions, respectively) are prepared and characterized by the X-ray diffraction technique. Crystals I are monoclinic, a = 18.599(4) Å, b = 12.556(3) Å, c = 14.042(3) Å, β = 102.90(3)°, V = 3196(1) ų, Z = 4, space group P2₁/c, R1 = 0.0278, wR2 = 0.0716, and Goof = 1.054 for 4982 reflections with I > 2σ(I). Structure I is built of the { Ca(H₂O)₄[Co(Nta)(Pic)]₂{ _1∞ polymer ribbons and molecules of crystallization water. One of the two symmetrically independent anionic complexes (B) is included in the chain and alternates with cationic units, whereas the other anionic complex (A) forms a branch of this chain. The cationic and anionic units are interlinked via the interactions of the Ca²⁺ cations with the carbonyl atoms of the main (Nta ^3?) and additional (Pic ^?1) ligands. The octahedral environment of the Co(III) atoms consists of donor atoms of the Nta ^3? (N + 3O) and Pic ^? (N + O) ligands. The coordination polyhedron of the Ca atom (pentagonal bipyramid) includes two carbonyl O atoms of two Nta ^3? ligands, one O_Pic atom, and four O_w atoms of water molecules.     

Synthesis and Luminescence Characteristics of LiMgAlF6:Ln3+ (Ln = Ce,Eu, Tb)

By solid state reaction, LiMgAlF₆ and LiMgAlF₆: Ln³⁺ are synthetized with the ratio 120/100/110 of LiF/MgF₂/AlF₃, at 1008 K, in high-purity Ar stream. Their crystal structure which belongs to hexagonal system are determined by X-Ray-Diffraction (XRD). Luminescence characteristics of Ce³⁺, Eu³⁺, Tb³⁺ and sensitization of Ce³⁺ to Tb³⁺ in LiMgAlF₆ are studied. It is shown that the sensitization of Ce³⁺ to Tb³⁺ is efficient and a bright green emission is observed.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Absorption and Circular Dichroism Spectra of La<Subscript>3</Subscript>Ga<Subscript>5</Subscript>SiO<Subscript>14</Subscript> Crystals Doped with Pr<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript>, and Er<Superscript>3+</Superscript> Ions

The absorption and circular dichroism (CD) spectra of La₃Ga₅SiO₁₄ langasite crystals doped with Pr³⁺, Ho³⁺, and Er³⁺ ions have been studied in the wavelength range of 350–700 nm. The electronic transitions of these ions, which replace La3+ ions in the 3e position with the symmetry 2, are observed in the spectra. All transitions are active in both the absorption and CD spectra. The dipole strengths D _om, rotational strengths R _om, and anisotropy factors g have been calculated for well-resolved bands. Some features are noted for the spectra that were obtained, and their relationship with the structure disorder is considered     

Visible up-conversion photoluminescence from IR diode-pumped SiO2–TiO2 nano-composite films heavily doped with Er3+–Yb3+ and Nd3+–Yb3+

Efficient infrared-to-visible conversion is reported in thin film nano-composites, with composition 90% SiO₂–10% TiO₂, fabricated by a spin-coating sol–gel route and co-doped with Er³⁺ Yb³⁺ and with Nd³⁺:Yb³⁺ ions. The conversion process is observed under 808 nm laser diode excitation and results in the generation of green (526 and 550 nm) and red (650 nm) emissions: from the former, and blue (478 nm) and green (513 and 580 nm) emissions from the latter. The main mechanism that allows for up-conversion is ascribed to energy transfer among Er³⁺ and Yb³⁺ ions in their excited states. Up-conversion efficiency for red emission predominates in samples doped with Er³⁺:Yb³. The results illustrate the large potential of this class of materials for photonic applications in optoelectronics devices.     

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO₂(n-C₃H₇COO)₂(H₂O)₂ (I) and Mg(H₂O)₆[UO₂(n-C₃H₇COO)₃]₂ (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P2₁/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group $Pa\bar 3$ , Z = 4, and R = 0.0173. The main structural units of I and II are [UO₂(C₃H₇COO)₂(H₂O)₂] molecules and [UO₂(C₃H₇COO)₃]^? anionic complexes, respectively, which belong to AB ₂ ⁰¹ M ₂ ¹ (I) and AB ₃ ⁰¹ (II) crystal chemical groups of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₇COO^?, and M ¹ = H₂O). A crystal chemical analysis of UO₂ L ₂ · nH₂O compounds, where L is a carboxylate ion, is performed.