Correlation between structural and optical properties of TiO<Subscript>2</Subscript>:ZnO thin films prepared by sol–gel method

We have studied structural and optical properties of thin films of TiO₂, doped with 5% ZnO and deposited on glass substrate (by the sol–gel method). Dip-coated thin films have been examined at different annealing temperatures (350–450 °C) and for various layer thicknesses (89–289 nm). Refractive index, porosity and energy band gap were calculated from the measured transmittance spectrum. The values of the index of refraction are in the range of 1.97–2.44, the porosity is in the range of 0.07–0.46 and the energy band gap is in the range of 3.32–3.43. The coefficient of transmission varies from 50 to 90%. In the case of the powder of TiO₂, doped with 5% ZnO, and aged for 3 months in ambient temperature, we have noticed the formation of the anatase phase (tetragonal structure with 20.23 nm grains). However, the undoped TiO₂ exhibits an amorphous phase. After heat treatments of thin films, titanium oxide starts to crystallize at the annealing temperature 350 °C. The obtained structures are anatase and brookite. The calculated grain size, depending on the annealing temperature and the layer thickness, is in the range of 8.61–29.48 nm.     

The influence of polyvinylpyrrolidone on thick and optical properties of BaTiO<Subscript>3</Subscript>:Er<Superscript>3+</Superscript> thin films prepared by sol–gel method

Erbium (Er³⁺) 0.5% mol doped barium titanate (BaTiO₃) thin films were elaborated via sol–gel method and dip-coating technique using titanium alkoxide and barium pentanedionate. Two syntheses were performed [with and without polyvinylpyrrolidone (PVP)] in order to obtain thick films. The BaTiO₃:Er³⁺ thin films prepared from the sol with PVP were elaborated with 1 layer and those without PVP and were elaborated with 17 layers. In both cases, the films were deposited on silica quartz substrates. Both BaTiO₃:Er³⁺ films presented a cubic phase, as determined by X-ray diffraction. BaTiO₃:Er³⁺ films elaborated with PVP via single-step dip coating produced crack-free films with thicknesses of ~800 nm. SEM micrographs for the obtained BaTiO₃:Er³⁺ films revealed high homogeneity and density. Mapping images obtained from BaTiO₃:Er³⁺ revealed homogeneous distribution of Er³⁺ ions on the surface. XPS analyses of the chemical state and chemical environment of the constituent elements in the compositions showed that Er³⁺ ions in (Ba_1−x Er _x )TiO₃ are in mixed valence of Er³⁺/Er²⁺. The BaTiO₃:Er³⁺-PVP film exhibited luminescent properties under near-infrared excitation, as revealed by green emissions. The BaTiO₃:Er³⁺-PVP film has good potential for optical applications.     

Single-phased white-light emitting CaAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>: Eu<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript> phosphors prepared by a sol–gel method

CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors have been prepared by a sol–gel method. X-ray diffractometer, spectrofluorometer and UV–Vis spectrometer were used to characterize structural and optical properties of the samples. The results indicate that anorthite (CaAl₂Si₂O₈) directly crystallizes at 1000 °C in the sol–gel process. CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors show two emission bands excited by ultraviolet light. Blue (around 415 nm) and yellow (around 575 nm) emissions originate from Eu²⁺ and Mn²⁺, respectively. With appropriate tuning of Mn²⁺ content, CaAl₂Si₂O₈: Eu²⁺, Mn²⁺ phosphors exhibit different hues and relative color temperatures.     

Synthesis of Ca<Subscript>3</Subscript>Al<Subscript>6</Subscript>Si<Subscript>2</Subscript>O<Subscript>16</Subscript>: Ce<Superscript>3+</Superscript>, Tb<Superscript>3+</Superscript> phosphors by sol–gel method and optical properties

Ca₃Al₆Si₂O₁₆: Ce³⁺, Tb³⁺ phosphors have been prepared by sol–gel method. The structure and photoluminescence properties were studied with careful. The results indicated that the single-phased Ca₃Al₆Si₂O₁₆ phosphors crystallize at 1,000 °C for 2 h in conventional furnace. With appropriate concentrations of Ce³⁺ and Tb³⁺ ions into Ca₃Al₆Si₂O₁₆ matrix, these materials exhibit blue phosphors and white light under ultraviolet radiation. White-light emission can be achieved because of a 400 nm emission ascribed to transitions of Ce³⁺ ions and three sharp peaks at 487, 543, 585 nm, respectively, resulting from transitions of Tb³⁺ ions.     

Structure and multiferroic properties of Bi<Subscript>5</Subscript>FeTi<Subscript>3</Subscript>O<Subscript>15</Subscript> thin films prepared by the sol–gel method

The Bi₅FeTi₃O₁₅ (BFTO) films of layered structure have been fabricated on Pt/Ti/SiO₂/Si substrates by the sol–gel method. The thermal decomposition behaviors of precursor powder were examined using thermo-gravimetric and differential scanning calorimeters analysis. The optimal heat treatment process for BFTO films were determined to be low-temperature drying at 200 °C for 4 min and high-temperature drying at 350 °C for 5 min followed by annealing at 740 °C for 60 min, which led to the formation of compact films with uniform grains of ~300 nm. The structural, surface topography, ferroelectric and magnetic properties of the films were investigated. The remnant polarization (2P _r) of BFTO thin films under an applied electric field of ~550 kV/cm are determined to be 67.5 μC/cm² . Meanwhile, the weak ferromagnetic properties of the BFTO films were observed at room temperature.     

Sol–gel synthesis of Eu<Superscript>3+</Superscript>: Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> nanophosphor

Eu (0.1, 0.5 and 1.0 mol%) doped Tb₃Al₅O₁₂ (TAG) was prepared by sol–gel technique through nitrate-citrate route followed by sintering in air (1,100 °C maximum temperature). XRD analysis showed that Eu³⁺ enters the TAG lattice substitutionally replacing the Tb³⁺ ion. Both XRD as well as FTIR investigation showed improvement in crystalline phase with the increase in the sintering temperature. SEM and TEM analysis showed that the powder contains the particles in 5–20 nm size with almost spherical morphology. The excitation spectrum recorded in 300–500 nm showed dominant absorption due to Tb³⁺ while the emission spectra recorded with 380 nm excitation had strong red emission characteristic of Eu³⁺. The intensity of this emission increases with the increase of the Eu concentration from 0.1 to 0.5 mol%. However, the emission intensity decreased on further increase in Eu concentration to 1.0 mol%. This intensity variation with dopant concentration is attributed to well-known “concentration quenching” observed in rare-earth doped materials. Reasonably strong red emission due to Eu was observed when excited with the blue (480 nm) radiation of a Xe lamp indicating the usefulness of the material for the realization of white light LED.     

Sol–gel elaboration and structural investigations of Lu<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> planar waveguides

Europium actived Lu₂O₃ sol–gel transparent and crack free films were deposited by dipping on silica substrates. The film microstructure was studied by waveguide Raman spectroscopy (WRS) with annealing temperatures from 400 up to 1,000 °C and X-ray diffraction. The WRS results and TEM observations were correlated and showed that crystallization of the lutetium oxide phase into cubic phase occurs at 600 °C and is stable up to 1,000 °C, the crystallite size increasing between ±38 nm with annealing temperature ranging from 600 to 1,000 °C. Opto-geometrical parameters were determined by m-lines spectroscopy using four different wavelengths of laser sources in order to confirm the step-index profile of the as-prepared waveguides. The Eu³⁺ doped films heat-treated at 1,000 °C presented a constant thickness for the wavelengths 493, 543, 594 and 632.8 nm and a density of 8.4 g cm⁻³. High-resolution X-ray images were obtained.     

Luminescence and long-lasting afterglow in Mn<Superscript>2+</Superscript> and Eu<Superscript>3+</Superscript> co-doped ZnO–GeO<Subscript>2</Subscript> glasses and glass ceramics prepared by sol–gel method

To develop new fluorescent and afterglow materials, Mn²⁺ and Eu³⁺ co-doped ZnO–GeO₂ glasses and glass ceramics were prepared by a sol–gel method and their optical properties were investigated by measuring luminescence, excitation and afterglow spectra, and luminescence quantum yield (QY). Under UV irradiation at 254 nm, some glasses and all of the glass ceramics showed green luminescence peaking at 534 nm due to the ⁴T₁ → ⁶A₁ transition of tetrahedrally coordinated Mn²⁺ ions. The strongest luminescence was observed in a glass ceramic of 0.1MnO–0.3Eu₂O₃–25ZnO–75GeO₂ heat treated at 900 °C, with QY of 49.8%. All of the green-luminescent glasses and glass ceramics showed green afterglow, and the afterglow lasting for more than 60 min was obtained in a glass ceramic heat treated at 900 °C. It is considered that the Eu³⁺ ions may behave as electron trapping centers to be associated with the occurrence of the green afterglow due to the Mn²⁺ ions in the co-doped system.     

Strong visible up-conversion emissions and thermometric applications of Er<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> codoped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> prepared by the sol–gel method

The Er³⁺–Yb³⁺ codoped Al₂O₃ has been prepared by the sol–gel method using the aluminium isopropoxide [Al(OC₃H₇)₃]-derived Al₂O₃ sols with addition of the erbium nitrate [Er(NO₃)₃ · 5H₂O] and ytterbium nitrate [Yb(NO₃)₃ · 5H₂O]. The phase structure, including only two crystalline types of doped Al₂O₃ phases, θ and γ, was obtained for the 1 mol% Er³⁺ and 5 mol% Yb³⁺ codoped Al₂O₃ at the sintering temperature of 1,273 K. By a 978 nm semiconductor laser diodes excitation, the visible up-conversion emissions centered at about 523, 545, and 660 nm were obtained. The temperature dependence of the green up-conversion emissions was studied over a wide temperature range of 300–825 K, and the reasonable agreement between the calculated temperature by the fluorescence intensity ratio (FIR) theory and the measured temperature proved that Er³⁺–Yb³⁺ codoped Al₂O₃ plays an important role in the application of high temperature sensor.     

Photoluminescence and photocatalytic properties of Er<Superscript>3+</Superscript>-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films prepared by sol–gel: application to Rhodamine B degradation under solar light

The effect of Er³⁺ doping (1%) on the structural, optical and photocatalytic properties of In₂O₃ thin films deposited on quartz substrates by spin coating was investigated. The In₂O₃:1% Er³⁺ films, annealed in the temperature range 800–1000 °C, were characterized by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy, UV–Vis spectroscopy, ellipsometry and photoluminescence (PL). The films are polycrystalline with a cubic structure and the lattice parameter increases with the incorporation of Er³⁺ owing to its larger radius. The SEM images of the film show a granular morphology with large grains (~ 200 nm). The doped In₂O₃ film exhibits less transparency than In₂O₃ in the UV–visible region with band gaps of 3.42 and 3.60 eV, respectively. PL shows strong lines at 548 and 567 nm, assigned to Er³⁺ under direct excitation at 532 nm. The energy diagram of the junction In₂O₃:1% Er³⁺/Na₂SO₄ (0.1 M) solution plotted from physical and photoelectrochemical characterizations shows the feasibility of the films for Rhodamine B (RhB) degradation under solar light. The conduction band at 2.22 V deriving from the In³⁺:5s orbital is suitably positioned with respect to the O₂/O ₂ ^· level (~ 1.40 V_SCE), leading to oxidation of 32% of 10 ppm RhB within 40 min of solar irradiation.     

Colour tuneability and white light generation in Yb<Superscript>3+</Superscript>–Ho<Superscript>3+</Superscript>–Tm<Superscript>3+</Superscript> co-doped SiO<Subscript>2</Subscript>–LaF<Subscript>3</Subscript> nano-glass-ceramics prepared by sol–gel method

Nanostructured transparent glass-ceramics with composition of 95SiO₂–5LaF₃ co-doped with 0.3Yb³⁺, 0.1Ho³⁺ and 0.1Tm³⁺ (mol%) were synthesized by thermal treatment of precursor sol–gel derived glasses. X-ray diffraction and transmission electron microscopy analysis point out the precipitation of hexagonal LaF₃ nanocrystals with diameter ranging from 11 to 20 nm in these nano-glass-ceramics. White light generation by means of efficient blue, green and red up-conversion luminescence under infrared excitation at 980 nm was observed and involved mechanisms were analyzed. Colour tuneability is achieved by varying the up-conversion emission ratios as a function of pump power.     

Characterization of TiO<Subscript>2</Subscript> powders and thin films prepared by non-aqueous sol–gel techniques

Stable TiO₂ sols were prepared using two non-aqueous sol–gel processes with titanium n-butoxide and titanium isopropoxide, respectively. Crystallization and phase transitions of powders and thin films were studied by ex situ and in situ X-ray diffraction. For both methods, TiO₂ began to crystallize around 320 °C in air. Using helium instead of air during heat treatment slowed down the crystallization and substoichiometric powders were formed. TiO₂ thin films were obtained by spin coating. The morphology of the films was evaluated using scanning electron microscopy. The films were homogeneous and transparent in the visible range. The effect of the heating atmosphere and the type of substrate was investigated.     

Flame synthesized Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> phosphors as spectral convertors for solar cells

Near-infrared (NIR) quantum cutting phosphors serve as a potential material for fabricating photovoltaic spectral convertors. In many cases, quantum cutting phosphors are obtained via a wet chemical method coupled with a post-annealing treatment—a very costly process. In this report, we used continuous flame spray pyrolysis (FSP) for fabricating Y₂O₃:Tb³⁺–Yb³⁺ quantum-cutting phosphors without any post-treatment. Based on characterizations by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we found that as-synthesized Y₂O₃:Tb³⁺–Yb³⁺ phosphors exhibit hollow and shell-like micro-structures composed of highly crystalline and pure cubic-phase nanoparticles (< 50 nm). Photoluminescence studies of the phosphors revealed that NIR emissions appeared with the introduction of Yb to Y₂O₃:Tb³⁺. Phosphor size was successfully controlled by managing the concentration of the metal precursor solution for FSP. The Y₂O₃:Tb³⁺–Yb³⁺ phosphors were then embedded into transparent poly-ethylene-co-vinyl acetate (EVA) film to form a spectral convertor. The composite films of Y₂O₃:Tb³⁺–Yb³⁺ phosphors and poly-EVA were found to be highly transparent in the visible range (> 500 nm), making them suitable as spectral photovoltaic convertors.     

Dielectric,ferroelectric and optical properties of BaZr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>O<Subscript>3</Subscript> thin films prepared by sol–gel-hydrothermal process

BaZr_0.2Ti_0.8O₃ thin films on Pt/Ti/SiO₂/Si substrates have been fabricated under low temperature conditions by a sol–gel-hydrothermal technique. The dielectric constant is 247–83 in the frequency range of 1 kHz–1 MHz. The corresponding dielectric loss is ~10⁻². The capacitance–voltage curve shows strong non-linear dielectric behavior leading to a high tunability, up to ~30% at 1 kHz. The remanent polarization and coercive field at room temperature are measured to be ~1.5 μC/cm² and ~90 kV/cm. The infrared optical properties of the thin films are investigated using an infrared spectroscopic ellipsometry in the wave number range of 800–4,000 cm⁻¹. Optical constants of the thin films are simultaneously obtained.     

Preparation of nanostructured thin films of yttrium iron garnet (Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript>) by sol–gel technology

The synthesis of hydrolytically active heteroligand coordination compounds [M(C₅H₇O₂)_3?x(C₅H₁₁Oⁱ)_x] (M = Fe³⁺ and Y³⁺) using iron and yttrium acetylacetonates has been studied. The gel formation kinetics in solutions of these compounds upon hydrolysis and polycondensation has also been studied. Thin films of a solution of these precursors have been applied to polished sapphire substrates by dip coating technology. The crystallization of nanostructured yttrium iron garnet (Y₃Fe₅O₁₂) films during heat treatment of xerogel coatings under various conditions has been studied. How the phase composition, microstructure, and particle size depend on the synthesis parameters has been recognized.     

Surface chemical bonding states and ferroelectricity of Ce-doped BiFeO<Subscript>3</Subscript> thin films prepared by sol–gel process

Bi_1−x Ce _x FeO₃ (x = 0, 0.05, 0.1, 0.15 and 0.20) (BCFO) thin films were deposited on Pt/TiN/Si₃N₄/Si substrates by sol–gel technique. Crystal structures, surface chemical compositions and bonding states of BCFO films were investigated by X-ray diffraction and X-ray photoelectron spectroscopy (XPS), respectively. Compared to BiFeO₃ (BFO) counterparts, the fitted XPS narrow-scan spectra of Bi 4f_7/2, Bi 4f_5/2, Fe 2p_3/2, Fe 2p_1/2 and O 1s peaks for Bi_0.8Ce_0.2FeO₃ film shift towards higher binding energy regions by amounts of 0.33, 0.29, 0.43, 0.58 and 0.49 eV, respectively. Dielectric constants and loss tangents of the BCFO (x = 0, 0.1 and 0.2) film capacitors are 159, 131, 116, 0.048, 0.041 and 0.035 at 1 MHz, respectively. Bi_0.8Ce_0.2FeO₃ film has a higher remnant polarization (P _r = 2.04 μC/cm²) than that of the BFO (P _r = 1.08 μC/cm²) at 388 kV/cm. Leakage current density of the Bi_0.8Ce_0.2FeO₃ capacitor is 1.47 × 10⁻⁴ A/cm² at 388 kV/cm, which is about two orders of magnitude lower than that of the BFO counterpart. Furthermore, Ce cations are feasibly substituted for Bi³⁺ in the Bi_0.8Ce_0.2FeO₃ matrix, possibly resulting in the enhanced ferroelectric properties for the decreased grain sizes and the reduced oxygen vacancies.     

Preparation of Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin films by sol–gel technique

In this study we describe the preparation of Ga₂Se₃ semiconductor compound thin films by sol–gel method for different crystal formation temperatures. The films were characterized by X-ray diffraction analyses (XRD), UV–visible spectrometer, and scanning electron microscope (SEM). The XRD spectrum showed that the formation of Ga₂Se₃ crystals were between 743 and 823 K. The thin film crystals that were formed at 773 K corresponded to the β phase and the preferred crystal structure was monoclinic. The value of band gap from optical absorption spectra for the Ga₂Se₃ thin films was estimated to be about E _g ~ 2.56 eV. The thickness of the one-coat Ga₂Se₃ thin films, which was measured by a Spectroscopic Ellipsometer, was about ~200 nm. The average grain sizes of scattered particles were within the limits between 200 and 500 nm.     

Bright blue pigment CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystals prepared by modified sol–gel method

Nanocrystalline films of magnetite have been prepared by a novel sol–gel route in which, a solution of iron (III) nitrate dissolved in ethylene glycol was applied on glass substrates by spin coating. Coating solution showed Newtonian behaviour and viscosity was found as 0.0215 Pa.s. Annealing temperature was selected between 291 and 350 °C by DTA analysis in order to obtain magnetite films. In-plane grazing angle XRD and TEM studies showed that magnetite phase was present upon annealing the films at 300 °C. The films had crack free surfaces and their thicknesses varied between ~10 and 200 nm. UV–Vis spectrum results showed that transmittance of the films increases with decreasing annealing temperature and increasing spinning rate. Up to 96% transmittance was observed between the wavelengths of 900–1,100 nm. Vibrating sample magnetometer measurements indicated that magnetite thin films showed ferromagnetic behavior and the saturation magnetization value was found as ~35 emu/cm³.