Sol-Gel Processing and Luminescent Properties of Rare-Earth Oxyfluoride Materials

Luminescent rare-earth oxyfluoride materials were prepared by a sol-gel method using trifluoroacetic acid as a fluorine source. Crystalline (La, Eu)OF powders and thin films were obtained by heating gels at typically 600–800°C. Transparent SiO₂-LaOF glass-ceramic thin films were also prepared by mixing the trifluoroacetate sols and silica sols, spin-coating on silica glass substrates and heating at temperatures 600–900°C. Eu³⁺ ions doped in the oxyfluoride materials exhibited a strong red ⁵D₀ ⁷F₂ emission (611 nm) by a charge-transfer (O^2–-Eu³⁺) excitation with ultra-violet radiation (265 nm). It was strongly suggested that the Eu³⁺ activators were preferentially incorporated into the crystalline LaOF phase in the SiO₂-LaOF glass-ceramics.     

Radioluminescence of Europium(III) in POCl3–SnCl4–235UO2+ 2–Eu3+, and D2O–235UO2+ 2–Eu3+ Solutions

Results of studying the spectral and luminescent properties of Eu³⁺ ions upon homogeneous excitation of POCl₃–SnCl₄–^-UO²⁺ ₂–Eu³⁺ and D₂O–²³⁵UO²⁺ ₂–Eu³⁺ solutions by -particles are presented. It was found that the radioluminescence intensity of Eu³⁺ ions in both solvents increases proportionally to the energy input by -particles. The yield of radioluminescence photons from europium ions in the POCl₃–SnCl₄–UO²⁺ ₂–Eu³⁺ solutions is more than nine times as high as that in D₂O–UO²⁺ ₂–Eu³⁺. The radiation-chemical yields of excited ⁵ D ₀ states of Eu³⁺ ions are 0.74 ± 0.07 and 0.18 ± 0.02 ions/100 eV in POCl₃–SnCl₄–UO²⁺ ₂–Eu³⁺ and D₂O–UO²⁺ ₂–Eu³⁺ solutions, respectively.     

Effect of the Excitation of the 4f Shell of Eu(fod)3 on the Formation of Complexes with 1,10-Phenanthroline

The effect of the electronic excitation of the -diketonate Eu(fod)₃ (fod is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedione-3,5) on complexation with 1,10-phenanthroline (phen) in benzene solutions was studied. The excitation of the f–f transitions of Eu³⁺ increased the stability of the Eu(fod)₃ · phen complex, thus providing direct evidence for the involvement of the 4f shell of Eu³⁺ in chemical bonding. The thermodynamic parameters of complexation were determined. The temperature quenching of Eu(fod)₃ · phen luminescence was studied.     

Determination of trace europium(III) based on a new fluorescence enhancement system of europium(III) with N,N′-<Emphasis Type="Italic">bis</Emphasis>-(4-N-aminothiourea-2-amylidene)-4,4′-diaminodiphenyl sulfone by EDTA or alumin in N,N-dimethylformamide

A new bis-Schiff base ligand, N,N-bis-(4-N-aminothiourea-2-amylidene)-4,4-diaminodiphenyl sulfone (ARADS), was synthesized. The solutions of its complex with Eu³⁺ in DMF can emit the intrinsic fluorescence of Eu³⁺. The fluorescence intensity of the complex was enhanced 20–30-fold in the presence of EDTA (or alum). The influence of seven kinds of solvents (DMF, CH₃CN, THF, acetone, CH₃OH, C₂H₅OH, and DMSO) on the intensity of fluorescence was studied. The results showed that the Eu³⁺-ARADS-EDTA (or alum) system emits its strongest fluorescence in DMF. Thus, the system can be used to develop a new method for the determination of europium(III). The excitation and emission wavelengths are 395 and 615 nm, respectively. Under optimal conditions, the fluorescence intensities vary linearly with the concentration of Eu³⁺ in the range 6.0 × 10^–10–5.2 × 10^–5 mol/L, with a detection limit of 5.0 × 10^–10 mol/L. The interference from some rare earth metals and other inorganic ions are described. The method is a selective, sensitive, rapid, and simple analytical procedure for the determination of europium(III) in high-purity yttrium oxide and synthetic samples. The mechanism of fluorescence enhancement was also studied.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 4, 2005, pp. 372–377.Original English Text Copyright © 2005 by Tianlin Yang, Wenwu Qin, and Weisheng Liu.The article was submitted by the authors in English.     

Textured PbTiO3, Pb(Ca)TiO3-Al2O3 Composite Films Prepared by Chemical Solution Deposition Method

Chemical solution deposition method (CSD) method was used to prepare PbTiO₃ (PT), Pb_{1– x} Ca _x TiO₃ (PCT), PbTiO₃-Al₂O₃ (PT-AL) and Pb_{1 – x} Ca _x TiO₃-Al₂O₃ (PCT-AL) thin films on amorphous (soda-lime glass, SiO₂ glass) substrates. The films were examined by XRD methods to describe the phase composition, cell parameters, type and degree of texture. In dependence on the molar ratio of Ti:Al, the different extent of crystallographic ordering was observed ranging from randomly oriented to strongly textured crystallites of PT. (100)uvw preferred orientation growth of PT grains was identified.     

Reddish-orange,neutral and warm white emissions in Eu3+, Dy3+ and Dy3+/Eu3+ doped CdO-GeO2-TeO2 glasses

Eu³⁺, Dy³⁺ and Dy³⁺/Eu³⁺ doped CdO-GeO₂-TeO₂ glasses were prepared using the melt-quenching process and analyzed by X-diffraction, Raman spectroscopy, excitation and emission spectra, and emission decay time profiles. The lack of X ray diffraction peaks revealed that all samples are amorphous. Vibrational modes associated with TeOTe and GeOGe related bonds and molecular oxygen were detected by Raman spectroscopy. The luminescence characteristics were studied upon excitations that correspond with the emission of InGaN (370–420 nm) based LEDs. The Eu³⁺ singly doped glass displayed reddish-orange global emission, with x = 0.601 and y = 0.349 CIE1931 chromaticity coordinates, upon 393 nm excitation. Neutral emission with x = 0.373 and y = 0.412 CIE1931 chromaticity coordinates and correlated color temperature (CCT) of 4400 K, was achieved in the Dy³⁺ singly doped glass excited at 388 nm. The Dy³⁺/Eu³⁺ co-doped glass exhibited warm, neutral and soft warm white emissions with CCT values of 3435, 4153 and 2740 K, under excitations at 382, 388 and 393 nm, respectively, depending mainly on the Dy³⁺ and Eu³⁺ relative excitation. The Dy³⁺ excitation bands observed in the Dy³⁺/Eu³⁺ glass by monitoring the 611 nm Eu³⁺ emission, suggest that Dy³⁺ → Eu³⁺ energy transfer takes place, despite the fact that the Dy³⁺ emission decays in the Dy³⁺ and Dy³⁺/Eu³⁺ doped glass, remain without changes. The shortening of Eu³⁺ decay in presence of Dy³⁺ was attributed to an Eu³⁺ → Dy³⁺ non-radiative energy transfer process, which according with the Inokuti-Hirayama model might be dominated through an electric quadrupole-quadrupole interaction, with efficiency and probability of 5.5% and 51.6 s⁻¹, respectively.     

Effect of Niobium Modifications to PZT (53/47) Thin Films Made by a Sol-Gel Route

Niobium-modified lead zirconate titanate thin films (PNZT) with nominal compositions, Pb_(1–0.5x) (Zr_0.53 Ti_0.47)_1–x Nb _x O₃:x = 0.02–0.07, have been prepared using a diol based sol-gel route. Single-layer (0.5 m) films were fabricated on platinised silicon substrates by spin-coating. The effect of niobium additions with regard to phase development, microstructure, and ferroelectric and dielectric properties were investigated for different annealing temperatures. For comparison, unmodified PZT films were also prepared. Niobium substitution increased the crystallisation temperatures for perovskite PNZT phase formation. The values of remanent polarisation P _r and dielectric constant _r were found to decrease with the introduction of Nb. For example, in films heated at 700°C for 15 min, the P _r value of an unmodified PZT film was 31 C cm^–2, compared to 17 C cm^–2 for an x = 0.05 PNZT film, whilst respective relative permittivity values fell from 1190 to 600. The highest Nb concentration film, x = 0.07, did not display any switchable polarisation characteristics, which is consistent with high levels of intermediate pyrochlore phase.     

Effect of the Measurement Temperature on the Dispersive Component of the Surface Free Energy of a Heat Treated SiO2 Xerogel

The surface free energy of a monolithic silica xerogel treated at 1000°C has been measured by inverse gas chromatography in the temperature range 25–150°C using n-alkanes. Values of the dispersive component, _S ^D, vary from 49.07 mJ·m^–2 at 25°C to 17.20 mJ·m^–2 at 150°C. The _S ^D value obtained at 25°C is lower than that found for amorphous and crystalline silicas but higher than that found for glass fibres meaning that the heat treatment at 1000°C changes drastically the structure of the silica xerogel showing a surface similar to a glass. However, the higher value of _S ^D in comparison to glass fibres can be attributed to the mesoporous structure present in the silica xerogel. In the temperature range of 60–90°C there exists an abrupt change of the _S ^D values as well as in the dispersive component of the surface enthalpy, h _S ^D. Such abrupt change can be attributed to an entropic contribution of the surface free energy.     

Electroconduction of Potassium Orthophosphate Modified with Triple-Charged Cations

Solid electrolytes in the systems K_{3 – 3x} Me _x PO₄ (Me = Sc, Y, In, La, Nd, Gd, Tb) are synthesized. Their phase composition and the temperature and concentration dependences of their electroconductivity are studied. In all the systems there form solid solutions based on K₃PO₄, which have a high potassium cation conductance. The latter is due to the formation of potassium vacancies at substitutions 3K⁺ Me³⁺ and, at lower temperatures, to stabilization of a high-temperature -modification of potassium orthophosphate. The electroconductivity of synthesized solid solutions, which equals (4–7) × 10^–3 and 10^–1 S cm^–1 at 300 and 700°C, is similar to that of solid electrolytes K_{3 – x} P_{1 – x} E _x ^VIO₄ and K_{3 – 4x} E _x ^IVPO₄.     

Mössbauer Spectroscopy and Radiofrequency Absorption Investigations of Pr Substituted 1-2-3 Type Compounds

⁵⁷Fe and ¹⁵¹Eu Mössbauer spectroscopy as well as RF susceptibility measurements were applied to study the effects of Pr substitution either into the rare earth or into the Ba site in Eu_1–x Pr _x Ba₂Cu₃O_7– and EuBa_2–x Pr _x Cu₃O_7–, respectively. Site mixing of Pr between the rare earth and Ba sites could be excluded by the utilization of ⁵⁷Fe Mössbauer spectroscopy. It was found that there exists a correlation between the ¹⁵¹Eu isomer shift and the onset temperature of the superconducting transition independent of the location of Pr. RF susceptibility measurements provide an evidence for a difference in the magnetic moment of Pr substituted for the Eu or Ba sites. The obtained results can be explained by hole filling as the dominant effect of Pr substitution.     

Preparation and Characterization of TiO2 Thin Films by Sol-Gel Method

Titanium dioxide (TiO₂) thin films have been deposited on silicon and glass substrates by the sol-gel process using titanium iso-propoxide [Ti(O-i-C₃H₇)₄]. The bond configuration of the TiO₂ thin films was analyzed by using FTIR in the wavenumber range from 400 to 4000 cm^–1. The spectral transmittance of as-deposited TiO₂ films deposited on fused silica glass was measured in the wavelength range from 200 to 900 nm. X-ray diffraction measurements were performed to determine the crystallinity of the TiO₂ films. As-deposited films were amorphous. As the film was annealed at higher temperature, the structure was transformed from amorphous to the anatase crystalline state. The chemical composition of the deposited film was investigated using X-ray photoelectron spectroscopy (XPS). The films are essentially stoichiometric with carbon as the dominant impurity on the surface. Raman spectra show the characteristic of TiO₂ anatase phase. The electrical properties of the TiO₂ films were measured using capacitance-voltage (C-V) and current-voltage techniques. From C-V measurements, the dielectric constants were calculated to be approximately 26 for the as-deposited films and 75–82 for films annealed at 700°C in different atmosphere. For the as-deposited samples, the breakdown voltage was 2.7 MV/cm, and for an electric field of 1 MV/cm, the leakage current was 5 × 10^–5 A/cm² and the resistivity was 2.2 × 10¹⁰ -cm.     

Analysis of Ti-N films by calibration of Ti X-ray spectra

Summary An energy-dispersive X-ray analysis of Ti_1–xN_x films was performed by using an Si(Li) detector. The Ti_1–xN_x films were sputtered on polished steel substrates in a mixed Ar+N₂ atmosphere by a reactive magnetron sputtering technique. Because the nitrogen X-ray line is absorbed by the Be window, an analysis method was developed based solely on the calibration of the characteristic Ti-K-intensities using a high-purity Ti standard. The film compositions were computed by means of a ZAF procedure. The samples closest to stoichiometric composition show maximum hardness.     

UV-Visible and IR Spectroelectrochemical Properties of V2O5 Crystalline Films Charged/Discharged in Extended Potential Range

Electrochemical properties of amorphous and crystalline V₂O₅ films, dip-coated from V-oxoisopropoxide sols and thermally treated at various temperatures (100, 150, 200 and 300°C), have been studied in extended potential range, i.e. from 1.4 to –1.6 V vs. Ag/AgCl in 1M LiClO₄/propylen carbonate (PC) electrolyte. The formation of various lithiated (-, -, - and -Li _x V₂O₅) phases was correlated with the values of insertion coefficient x obtained from cyclic voltammograms (CV) of crystalline V₂O₅ films (300°C). Reversible charging was observed when films were cycled up to –1.0 V vs. Ag/AgCl, while the extension of the potential to –1.3 V vs. Ag/AgCl change the CV of films irreversibly. Charging of crystalline V₂O₅ films was followed by the help of in-situ UV-visible spectroscopy, that revealed the intensity variations of the polaron absorption above 600 nm and the presence of the absorbing V³⁺ species between 550 and 650 nm. Ex-situ IR spectra of the crystalline films charged/discharged at –1.6V/1.4V vs. Ag/AgCl confirmed the amorphisation of the films' structure.     

New water-soluble and film-forming aminocellulose tosylates as enzyme support matrices with Cu<Superscript>2+</Superscript>-chelating properties

Within the framework of our studies on enzyme-compatible support matrix structures, we succeeded in making further derivatives of the new aminocellulose type P–CH₂–NH–(X)–NH₂ (P = cellulose); (X) = –(CH₂)₂– (EDA), –(CH₂)₂–NH–(CH₂)₂– (DETA), –(CH₂)₃–NH–(CH₂)₃– (DPTA), –(CH₂)₂–NH–(CH₂)₂–NH–(CH₂)₂– (TETA) accessible by nucleophilic substitution reaction with ethylenediamine (EDA) and selected oligoamines starting from 6(2)-O-tosylcellulose tosylate (DS_tosylate = 0.8). The ¹³C-NMR data show that the EDA and oligoamine residues are at C6 of the anhydroglucose unit (AGU) and that OH and tosylate are also (partially) present at C6. OH and partially tosylate are at C2/C3. All the synthesized aminocellulose tosylates were soluble in water and formed transparent films from their solutions. The aminocellulose tosylate solutions and the films prepared from them formed blue-coloured chelate complexes with Cu²⁺ ions, whose absorption maxima at wavelengths in the VIS region were located similarly to those of the Cu²⁺ chelate complexes with EDA and with the oligoamines. AFM investigations have shown that the aminocellulose films, depending on structural and environment-induced factors influencing e.g. SiO₂ polymer films, exhibit flat topographies (<1 nm), and on protonated NH₂ polymer films, such as aminopropyl-functionalized polysiloxane films, nanostructured topographies of derivative-dependent shape and nanostructure size as film supports in the form of nanotubes. The aminocellulose films could be covalently coupled with glucose oxidase enzyme by various known and novel bifunctional reactions via NH₂-reactive compounds. In this connection, it was confirmed again that the immobilized enzyme parameters, such as enzyme activity/area and K_M value, can be changed by the interplay of aminocellulose film, coupling structure and enzyme protein in the sense of an application-relevant optimization.     

Separation of cerium and europium by extraction with tributyl phosphate and di(2-ethylhexyl)phosphoric acid in n-alkane from nitrate solutions

The following extraction systems have been studied: (Ce³⁺+Eu³⁺) (NO₃)-(EDTA, DCTA, DTPA)/TBP in n-alkane and (Ce³⁺+Eu³⁺)(NO₃)/DEHPA in n-alkane at concentration ratios as follows: [Ce³⁺]=trace –1 mol·dm^–3, [Eu³⁺]=trace –0.1 mol·dm^–3. [TBP]=(0.183–1.83) mol·dm^–3, [DEHPA]=(5·10^–3–0.1) mol·dm^–3, [(H, Na)NO₃]=(0.1–6) mol·dm^–3, [Eu³⁺]: [EDTA, DCTA, DTPA]=11–110. The initial concentration of Eu³⁺ in aqueous phase in the extraction system containing a mixture of Ce³⁺ and Eu³⁺ was trace, 1% and 10% compared with the Ce³⁺ concentration. The distribution of the elements between the phases was observed radiometrically using¹⁴¹Ce,¹⁵²Eu and¹⁵⁴Eu. The results are documented by the distribution ratios D_Ce, D_Eu and separation factor =D_Eu/D_Ce as functions of variable parameters of the systems.     

Wetting of Solids by Aqueous Solutions of Surfactant Binary Mixtures: 2. Wetting of High-Energy Surface

Wetting of glass by aqueous solutions of binary mixtures of cationic and nonionic surfactants was studied in the range of overall concentrations c ₀ = 10^–8–10^–2 M at the molar fraction of cationic surfactant = 0.2, 0.5, and 0.8. It was established that the character of glass wetting is determined by the presence of cationic surfactant in the mixture: contact angle isotherms (c ₀) exhibit maximum, as in the case of individual cationic component solutions. Maximal values are virtually independent of the nature of cationic surfactant and its molar fraction in the mixture. It was shown that the synergistic effect in glass wetting is controlled by the chemical structure of surfactant cation.     

Optical Spectroscopy of Hybrid Sol-Gel Coatings Doped with Noble Metals

Sol-gel coatings in the xM (100-x) SiO₂ system, (M = Cu, Ag and Au) x =0.1–10 mol%), are deposited on soda lime glass slides by using silicon tetramethoxide Si(OCH₃)₄) and methyltriethoxysilane (SiCH₃[OCH₂CH₃]₃) as silica precursors. Anhydrous CuCl, CuCl₂ 2H₂O, Cu(NO₃)₂ 3H₂O, CuSO₄ 5H₂O, AgNO₃ and HAuCl₄ 3H₂O are used as copper, silver and gold sources. Coatings with thicknesses ranging from 100 to 900 nm are deposited on the subs trates by dip-coating and subsequently densified at 500°C for 1 h in air. Spectroscopic studies of the coatings as a function of the thicknesses and the metal concentration are carried out by photoluminescence (PL) and optical absorption (OA). In addition, direct observations of some gold coatings were performed by transmission electron microscopy (TEM). Results indicate that for silver and copper containing coatings the excitation and emission spectra arise from electronic transitions in Ag⁺ and Cu⁺ ions and no significant absorption bands due to colloidal precipitation are observed. Gold containing coatings show purple coloration due to an absorption peaking in the 520–560 nm range, which is characteristic of gold colloids. The presence of these colloids is confirmed by TEM observations.     

Electroconductivity of Potassium Orthophosphate Modified by Four-Charged Cations

Solid solutions based on K₃PO₄ in systems K_{3 – 4x} E" _x PO₄ (E" = Si, Ti, Ge, Zr, Sn, Hf, Ce) are synthesized. The crystal structure, thermal behavior, and electroconduction of the synthesized solutions is studied. The narrowest single-phase regions take place in the systems where E" = Si, Ge (x 0.025), and the widest, in the system with Zr (x 0.125, at 700°C). Introducing Ti or Sn additives (x 0.05) and minimum quantities of Zr, Hf, or Ce (x = 0.025) into potassium orthophosphate leads to stabilization of highly-conductive -modification of K₃PO₄ at room temperature. Maximum values of potassium-cation conduction in all the systems studied correspond to regions of single-phase solid solutions based on K₃PO₄. The maximum electroconductivity (0.005 S cm^–1 at 300°C, 0.1 S cm^–1 at 700°C) and the smallest activation energies (32–35 kJ mol^–1) take place in the systems with Zr and Hf.     

Photoluminescence study of the electronic structure of HfO<Subscript>2</Subscript> films

A method was developed for investigating hafnium dioxide films; this procedure uses a hydrogen-deuterium lamp as a source of photoluminescence (PL) excitation. Photoluminescence in HfO₂ films was investigated. An analysis of the PL spectra of the films showed that they coincided with the spectra described in the literature and recorded using more powerful sources (synchrotron radiation or ArF laser). A comparison of our results with the literature data confirmed that the PL spectra of the films weakly depended on the type of the substrate used for the synthesis. The PL band intensity depends on the synthetic conditions and the annealing temperature. We analyzed the PL and excitation spectra and revealed an emission band at an energy E ～ 4 eV with a narrow excitation maximum at E _max ? 4.25 eV, which was assigned to the vibronic resonance transition A ²Σ⁺ ? X ²Π_i in the OH_?* excited radical. Water was detected in the PL spectra of the HfO₂ films; it is trapped as an impurity after thermal decomposition of Hf(dpm)₄ in the course of film growth. The detection of water in the PL spectra of these films provides new insight into the problem of the effect of this impurity on the leakage currents and the importance of control over its content in the films.     

Linkage isomerism and redox properties of ruthenium–polypyridine benzotriazole complexes

A new series of mono- and di-substituted ruthenium–polypyridine complexes of the type cis-[Ru^III,II (bpy)₂(L1)(L2)] ^{n +} (L1 = Cl^–, bta or py; L2 = bta; bpy = 2,2-bipyridine; bta = benzotriazole; py = pyridine) has been prepared, isolated as hexafluorophosphate salts, and investigated in organic solutions by means of cyclic voltammetry and spectroelectrochemistry. The chemical oxidation of all the benzotriazole derivatives, starting from cis-[Ru^II(bpy)₂(L1)(bta)] ^x (x = +1 or +2), leads essentially to N(3)-bound products, i.e., cis-[Ru^III(bpy)₂ (L1)(N(3){bta})] ^x+1 isomers. Nevertheless, while the benzotriazole-monosubstituted species undergoes an intramolecular isomerization, N(3) N(2), accompanying the electrochemical reduction centered on the metal ion, Ru^III Ru^II, the disubstituted derivatives do not display any spectral or electrochemical evidence of linkage isomerism. The equilibrium and kinetic constants for the isomerization were determined from the cyclic voltammograms at several scan rates, according to an electrochemical–chemical (EC) coupling scheme. The data were compared with a set of constants and parameters obtained previously for a series of ruthenium and iron complexes. The experimental results were found to be quite consistent with theoretical calculations, and reflect the importance of -backbonding interactions in the stabilization of the metal-centered reduced state (M^II) on such species with low-spin d⁶ configuration.