Novel polymer–inorganic hybrid materials fabricated with in situ composition and luminescent properties

A new polymer–inorganic material was synthesized from terephthalic acid (TPA) and rare-earth ion (Tb³⁺, Eu³⁺) complex, which rare-earth ions connect with polymer by covalent bands. The luminescent europium and terbium coordination polymers, PET–Tb and PET–Eu, were produced in situ through low temperature solution polycondensation (PET = polyethyl terephthate ester). FTIR spectroscopy, ultraviolet absorption and scanning electron microscopy were applied to characterize the structure of obtained hybrid material. Phosphorescence and fluorescence spectra were applied to characterize the photophysical properties of the obtained hybrid material. The experimental result shows that the strong luminescence of rare-earth ions substantiates optimum energy match and effective intramolecular energy transfer between the triplet state energy of coordination complex and the emissive energy level of the rare-earth ions. The hybrid material systems can be expected to have potential applications in photophysical sensors.     

Optical and thermoluminescence properties of R2O–RF–B2O3 glass systems doped with MnO

Alkali fluoroborate glass systems containing manganese cations have been thoroughly investigated in order to obtain information about the structural role of manganese in such glass hosts. The amorphous phase of the prepared glass samples R₂O–RF–B₂O₃:MnO (with R = Li and Na) was confirmed from their X-ray diffraction. From the infrared spectra of these glass systems it was concluded that the glass structure contains two group of bands; one due to trigonal BO₃ units and the second due to the tetrahedral BO₄ units. As manganese was introduced, replacing lithium or sodium, it acts as a network modifier and the intensity of the second group of bands increases at the expense of the first group of bands. The optical absorption spectra of R₂O–RF–B₂O₃:MnO exhibited two conventional absorption bands; one due to Mn²⁺ ions and the other due to Mn³⁺ ions. The ESR spectra of these glasses showed a six-line hyper-fine structure centered at g = 2.01 (due to Mn²⁺ ions) and another signal at g = 4.3 (due to Mn³⁺ ions). The intensity of optical absorption bands and the ESR signal due to Mn²⁺ ions decreases with increasing MnO concentration indicating the conversion of Mn²⁺ ions into Mn³⁺ ions in the glass network. The thermoluminescence studies on these glass systems showed a quenching of TL output with increase in the concentration of MnO. All the obtained results were discussed on the basis of the glass structure and the conversion of Mn²⁺ into Mn³⁺ ions with increasing concentration of MnO in the glass systems.     

Lanthanide molecular-based hybrids covalently bonded with silica: Photoluminescence and control of micromorphology

The syntheses of modified 5-bromonicotinic acid by (3-aminopropyl)triethoxysilane and the preparation of their corresponding organic–inorganic molecular-based hybrid material with the two components equipped with covalent bonds are described. The organic moiety is a derivative of 5-bromonicotinic acid which is applied to coordinate to RE³⁺ and further introduced into silica matrices by Si–O bonds after hydrolysis and polycondensation processes. Judd–Ofelt theory proves that covalency increases along with increasing reciprocal energy difference between the 4fN and 4fN-15d1configurations. Ultraviolet absorption, phosphorescence and luminescence spectra were utilized to characterize the photophysical properties of the obtained hybrid material and the above spectroscopic data reveal that the triplet energy of modified 5-bromonicotinic acid matches with the emissive energy level of RE³⁺. In this way, the intramolecular energy transfer process took place within these molecular-based hybrids and strong green, red or blue emissions of RE³⁺ have been acquired. Scanning electronic microscope presents no phase separation phenomenon appear and the different crystal structures of lanthanide complex precursor molecules have influence on the microstructure and micromorphology of corresponding molecular hybrids.     

Optical properties and valence change of samarium ions in a sol–gel Al2O3–B2O3–SiO2 glass by femtosecond laser irradiation

10Al₂O₃–5B₂O₃–85SiO₂–xSm₂O₃ glasses were prepared by the sol–gel method. The emission spectra of the glasses indicate that the quench concentration of the Sm³⁺ ions is about 0.2 mol%. The emission spectra of the glasses after high-temperature treatment with H₂ gas exhibit the coexistence of the Sm³⁺ and Sm²⁺ ions. We observed the strong emission line of the Sm²⁺ ions and the emission band of the non-bridging oxygen hole center when the glasses were exposed to a femtosecond laser. It indicates that some Sm³⁺ ions were reduced to Sm²⁺ ions by femtosecond laser pulses and non-bridging oxygen hole centers were formed. The ⁵D₀–⁷F₀ emission line of the Sm²⁺ ions by femtosecond laser irradiation shows a red shift, compared with the emission of the Sm²⁺ ions by reduction with H₂ gas. The strong absorption band and weak, sharp absorption lines in the range from the UV to IR come from charge transfer and the transition from the ⁶H_5/2 state to the various excited states of the Sm³⁺ ions. The reduction mechanism of Sm³⁺ ions is discussed.     

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd–PSS films were processed using the acid of poly(styrene sulfonate) – H–PSS and neodymium nitrate – Nd(NO₃)₃; the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV–Vis–NIR spectral region presents typical electronic transitions of Nd³⁺ ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N–O groups in the range of 1400–720 cm^?1, prove the permanence of Nd(NO₃)_x, with x = 1, 2 and/or 3, in the H–PSS matrix. UV–Vis site selective photoluminescence data indicate that the incorporation of Nd³⁺ introduces a blue shift in PSS emission (325–800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd³⁺ reabsorption and energy transfer effects between the PSS matrix and Nd³⁺ were also observed. The IR emission of Nd–PSS films at 1076 nm (⁴F_3/2 → ⁴I_11/2) present constant efficiency, independent on Nd³⁺ concentration. The Judd–Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd³⁺. Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix.     

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     

Valence states and coordination of titanium ions in beryl crystals

The valence states and coordination of titanium ions in beryl crystals grown from flux and by gastransport reactions have been studied by the methods of electron paramagnetic resonance (EPR) and optical spectroscopy. The parameters of the EPR spectra for Ti³⁺ in the Al³⁺ and Si⁴⁺ sites are determined. It is found that at concentrations exceeding 0.1–0.15 wt %, the EPR-spectra have additional lines due to exchange-bonded pairs of Ti³⁺ ions. It is shown that the two-humped absorption band with the maxima at 495 (π), 545 (π), and 495 (π) nm are formed due to Ti³⁺ ions located in the octahedral position.     

Emission and local structure of rare-earth ions in chalcogenide glasses

Local structures of rare-earth ions in Ge–Ga–S–CsBr glasses were investigated to understand the structural origin on the emission property enhancement. The frequency of the phonon vibration controlling the multiphonon relaxation was changed to 245 cm⁻¹ due to the formation of Ga–Br bonds with CsBr addition to sulfide glasses. Formation of this new chemical bond was also confirmed from the phonon side band spectra of Eu³⁺ ions. Analyses of the EXASF spectra proved that Tm³⁺ ions were surrounded by approximately seven S ions in Ge_0.25Ga_0.10S_0.65 glass but were coordinated by ∼6 Br ions in the glass with 10 mol% of CsBr.     

EPR spectra of Cr3+-doped LuNbO4 crystals

Ferroelastic LuNbO₄ single crystals containing 0.3 at. % Cr³⁺ ions have been grown by the floating zone technique, and their EPR spectra have been studied at a frequency of 9.8 GHz at room temperature. The lines on the spectra are due to the transitions caused by three paramagnetic centers formed as a result of the replacement of one isovalent position of a Lu₃₊ ion and two nonisovalent positions of Nb₅₊ions by Cr₃₊-ions. As a result of twinning, the line number is doubled and four principal directions arise along which the same spectra are obtained. The spectra of these centers were described by a spin Hamiltonian with S = 3/2, the D and E parameters ranging from 0.024 to 0.17 cm^?1, and the g-factors g ∥ = 1.75–2.20 and g ⊥ = 1.90–2.13.     

Some features of EPR and optical spectra of vanadium in aluminophosphate glasses

The EPR and optical spectra of vanadium in glasses of ternary Al₂O₃P₂O₅SiO₂ and Al₂O₃P₂O₅B₂O₃ systems have been measured. The results were compared with earlier data for vanadium in binary phosphate, aluminophosphate and silicaphosphate glasses and with results of de-Biasi for V⁴⁺ in crystalline powder α-crystobalite AlPO₄. The superpositions of two hyperfine spectra (ASB-I and ASB-II) were found for many glasses of ternary systems. Both spectra can be attributed to VO²⁺ ions. The intensity ratio of the ASB-II spectrum to ASB-I depends on glass composition but is great (> 7) for all the glasses. Only the ASB-II spectrum was observed in glasses with low concentration of Al₂O₃. The spectral parameters of ASB-II spectrum are g_| = 1.916–1.921; g_⊥ 1.980–1.988; A_| = (188?190) × 10^?4cm^?1 and A_⊥ = (74–77) × 10^?4cm^?1. Three intense bands at 370, 455 and 700 ans 720 nm observed in these glasses can be attributed to V³⁺ ions. The excellent agreement of the parameters of the EPR spectrum of V⁴⁺ ions in crystalline α-crystobalite AIPO₄ and ASB-II spectra in the glasses under study suggest the identical electron structure of the paramagnetic species. This species is believed to be characterized by optical bands at 680 and 790 nm which have been observed by de Biasi. The orbital mixing coefficients indicate strong tetragonal distortion of vanadyl complexes responsible for the ASB-II spectrum. It is assumed that VO²⁺ ions responsible for this spectrum act as modifiers fitting into the relatively small holes of the three-dimensional networks of phosphate glasses containing no cations of large radii. The microscopic basicity of oxygens in such holes must be about 0.48.     

Synthesis and Judd-Ofelt analysis of a sol-gel material doped with a Ln2(Benzoate)6(Phen)2 (Ln = Er/Yb) complex

In this work, we have prepared a sol-gel derived hybrid material directly doped with Er_1.4Yb_0.6(Benzoate)₆(Phen)₂ (Phen = 1,10-phenanthroline) complex, which was reported with intramolecular Yb-Er energy-transfer process in our previous work. The infrared (IR) spectra of the pure complex and hybrid gel material were investigated. The NIR photoluminescence (PL) spectrum of hybrid gel material shows strong characteristic emission of Er³⁺ with broad full width at half-maximum (FWHM) of 70 nm. Judd-Ofelt theory was used in order to analyze the optical properties of Er³⁺ ions in the hybrid gel material.     

Structural characteristics of some lanthanide violurate complexes

The magnetic moments and the electronic spectra of violurate complexes of Ce³⁺, Pr³⁺, Pr⁴⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Ho³⁺, Er³⁺, and Yb³⁺ have been investigated. The solid complexes are paramagnetic and have magnetic moment values near to the ground state values of the free ions. Few cases differ, since there exist possible electronic transitions (4f → 5d) in case of Ce³⁺ complexes and (f → f) for Ho³⁺ and Dy³⁺ complexes. The magnetic measurements in connection with the electronic spectra were used to decide the different electronic structural configuration of elements and hence the configuration of the coordination polyhedra around the central metal ions of the investigated complexes.     

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.     

State of the chromium ion in soda silicate glasses under various oxygen pressures

Optical absorption and ESR spectra of chromium in soda silicate glasses were measured to characterize the electronic environment of the chromium ion in these glasses. Glasses produced in very strongly reducing conditions showed a broad optical absorption in the wavenumber range of 10 000–25 000 cm^?1 without any ESR absorption, which suggested the formation of Cr²⁺ ions. Glasses produced in air or moderately reducing conditions showed ESR signals suggesting that there are three different states of Cr³⁺ ions, the strongly coupled Cr³⁺ ion pairs, the weakly coupled Cr³⁺ ion pairs and the isolated Cr³⁺ ions in elongated tetragonal sites or sites with lower symmetry. The presence of Cr⁵⁺ ions in glasses produced in air was also suggested. It was indicated that the critical partial oxygen pressure of the formation of Cr²⁺ ions is in the vicinity of P_O2 = 10^?8 atm and that Cr²⁺ ions do not coexist with Cr³⁺ ions homogeneously in soda silicate glasses.     

Thermo-optical properties and nonradiative quantum efficiency of Er3+-doped and Er3+/Tm3+-co-doped tellurite glasses

Thermal lens (TL) measurements were performed in tellurite glasses, 70TeO₂–19WO₃–7Na₂O–4Nb₂O₅ (mol%), undoped, doped with Er³⁺ (1.19 × 10²⁰ ions/cm³) and co-doped with Er³⁺ (1.19 × 10²⁰ ions/cm³)/Tm³⁺ (1.56 × 10²⁰ ions/cm³). The absolute nonradiative quantum efficiency (ϕ) was determined by the TL method. The ϕ values for Er³⁺/Tm³⁺-co-doped and Er³⁺-doped tellurite glasses were 0.98 and 0.74, respectively. Fluorescence spectra were performed at λ_e = 488 nm and used to estimate the fluorescence quantum efficiency (η) using the TL results. These values were compared with results obtained by Judd–Ofelt calculations.     

Energy transfer from Bi3+ sensitizing the luminescence of Eu3+ in clusters embedded into sol–gel silica glasses

Y³⁺(La³⁺), Eu³⁺ and Bi³⁺ ions co-doped sol–gel silica glasses were synthesized. Photoluminescence spectra show that there is energy transfer from Bi³⁺ ions to the emission band of Eu³⁺ ions. The co-dopants Y³⁺ or La³⁺ have strong effects on the local structure and luminescence of Eu³⁺ ions. For 0.5 mol% Eu³⁺ ions doped glasses, the co-doping of 1 mol% Bi³⁺ and 1 mol% Y³⁺ is the most appropriate for the sensitization from Bi³⁺ to Eu³⁺. The sensitization effectiveness from Bi³⁺ ions to Eu³⁺ ions was studied by changing the amount of Bi³⁺ and Y³⁺, and clusters containing rare earth ions and Bi³⁺ ions dominate the energy transfer processes. The comparison of luminescent R-values (the intensity ratio of ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁ in Eu³⁺ ions) between glasses containing La³⁺ and containing Y³⁺ verifies the formation of clusters in sol–gel glasses. As a favorable configuration for energy transfer, the accurate design and synthesis of clusters-contained glasses may provide a new kind of luminescent materials.     

Spectroscopic properties of Cr3+ ions in nanocrystalline glass–ceramic composites

Luminescence properties of Cr³⁺ ions in a silica-based precursor glass, and in fabricated optically transparent glass-based nanocrystalline composites, have been investigated. The luminescence spectra of the precursor glass revealed a wide range of crystal fields and showed the ⁴T₂–⁴A₂ broadband emission of Cr³⁺ ions in a weak crystal field, combined with ²E–⁴A₂ emission characteristic for Cr³⁺ ions in a strong crystal field. Glass–ceramic nanocomposites, with gallium oxide nanocrystals nucleated in a host glass matrix, indicated the prevailing contribution of the crystal-like ²E–⁴A₂ emissions (R-lines) of Cr³⁺ ions in a strong crystal field. The low-temperature studies demonstrated that the fluorescence of Cr³⁺ ions could be altered from sharp R-lines of the ²E–⁴A₂ transition, below 70 K, to a combination of R-lines and their sidebands, above 70 K. Our results indicate that, in the developed glass–ceramic nanocomposites, most of the Cr³⁺ ions have migrated from the host glass matrix to the nucleated gallium oxide nanocrystalline phase.     

A pulsed EPR study of clustering of Yb ions incorporated in GeO2 glass

The structural aspects of clustering of Yb³⁺ ions and the paramagnetic behavior of these clusters have been investigated in GeO₂ glasses doped with 140-1100 ppm by weight of Yb₂O₃ using time-domain electron paramagnetic resonance (EPR) spectroscopic techniques. The echo-detected EPR (EDEPR) spectra of Yb³⁺ ions and their unusual dependencies on microwave power and magnetic field have been found to be indicative of the formation of clusters of these rare earth ions in GeO₂ glass that behave as non-Kramers type spin systems. The magnetic field and concentration dependence of phase relaxation rates of Yb³⁺ in these glasses further substantiate such a scenario and indicate the formation of clusters of Yb³⁺ ions. A comparison of the EDEPR spectra with calculated cw-EPR line shapes yields a semi-quantitative measure of the typical cluster size of ?3 Yb atoms and intra-cluster Yb-Yb distances of 3.5-4.0 Å in these glasses at doping levels of ?350 ppm of Yb₂O₃.     

Production and shaping of high performance phosphors by using the sol–gel process: Yttrium aluminum garnet (Y3Al5O12)

Luminescent Y₃Al₅O₁₂:Tb³⁺ (YAG:Tb³⁺) phosphor thin films and powders have been successfully prepared by the sol–gel route from alkoxide precursors. Advanced coatings were produced by spray and dip-coating from stabilized sols. X-ray diffraction (XRD), attenuated total reflectance/Fourier transform infrared spectroscopy (ATR/FTIR) and atomic force microscopy (AFM) were used to investigate the structure and morphology of layers. YAG phases of high purity were obtained for both powders and films. AFM study revealed coatings of homogeneous topography, whatever the deposition technique. However, dip-coated samples exhibited a much smoother topography, characterized by a root mean square (rms) roughness much lower than that of spray-coated ones. Laser induced emission spectra and decay times of Tb³⁺ ions in a spray-coated film were recorded. Measurements exhibit the characteristic green emission of Tb³⁺. Effectiveness of the Tb³⁺ doped coatings under UV excitation is also illustrated by pictures.     

Cr3+‐doped LiNbO3 crystals grown by the Bridgman method

The growth of LiNbO₃ crystals doped with Cr³⁺ ions in 0.1, 0.2, and 0.5 mol % concentrations by Bridgman method were reported. The Cr³⁺ ion concentrations in crystals were measured by inductively coupled plasma spectrometry. Electron paramagnetic resonance had been used to investigate the sites occupied by the Cr³⁺ ions. Two Cr³⁺ ion centers located at Li⁺ and Nb⁵⁺ sites (Cr_Li³⁺ and Cr_Nb³⁺ centers, respectively) were observed. Optical absorption and temperature‐dependence emission spectra of the Cr³⁺ ions were reported. The crystal‐field parameters and Racah parameters of the Cr³⁺ ion defect sites were reported and compared with those grown by Czochralski technique. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)