Al2O3–TiO2 thin films on glass substrate by sol–gel technique

In the present research, self-cleaning Al₂O₃–TiO₂ thin films were successfully prepared on glass substrate using a sol–gel technique for photocatalytic applications. We investigated the phase structure, microstructure, adhesion and optical properties of the coatings by using XRD, SEM, scratch tester and UV/Vis spectrophotometer. Four different solutions were prepared by changing Al/Ti molar ratios such as 0, 0.07, 0.18 and 0.73. Glass substrates were coated by solutions of Ti-alkoxide, Al-chloride, glacial acetic acid and isopropanol. The obtained gel films were dried at 300 °C for 10 min and subsequently heat-treated at 500 °C for 5 min in air. The oxide thin films were annealed at 600 °C for 60 min in air. TiO₂, Ti₃O₅, TiO, Ti₂O, α-Al₂O₃ and AlTi phases were determined in the coatings. The microstructural observations demonstrated that Al₂O₃ content improved surface morphology of the films and the thickness of film and surface defects increased in accordance with number of dipping. It was found that the critical load values of the films with 0, 0.07, 0.18 and 0.73 Al/Ti molar ratios were found to be 11, 15, 22 and 28 mN, respectively. For the optical property, the absorption band of synthesized powders shifted from the UV region to the visible region according to the increase of the amount of Al dopant. The oxide films were found to be active for photocatalytic decomposition of methylene blue.     

Fabrication of LiCoO2 thin film cathodes by DC magnetron sputtering method

LiCoO₂ thin films were fabricated on Al substrate by direct current magnetron sputtering method. The effects of Ar/O₂ gas rates and annealing temperatures were investigated. Crystal structures and surface morphologies of the deposited films were investigated by X-ray diffraction, Raman scattering spectroscopy and field emission scanning electron microscopy. The as-deposited LiCoO₂ thin films exhibited amorphous structure. The crystallization starts at the annealing temperature over 400 °C. However, the annealed films have the partially disordered structure without completely ordered crystalline structure even at 600 °C annealing. The electrochemical properties of the LiCoO₂ films were investigated by the charge–discharge and cycle measurements. The 500 °C annealing film has the highest capacity retention rate of 78.2% at 100th cycles.     

Studies on optical,chemical, and electrical properties of rapid SiO2 atomic layer deposition using tris(tert-butoxy)silanol and trimethyl-aluminum

Rapid SiO₂ atomic layer deposition (ALD) was used to deposit amorphous, transparent, and conformal SiO₂ films using tris(tert-butoxy)silanol (TBS) and trimethyl-aluminum (TMA) as silicon oxide source and catalytic agent, respectively. The growth rate of the SiO₂ films drastically increased to a maximum value (2.3 nm/cycle) at 200 °C and slightly decreased to 1.6 nm/cycle at 275 °C. The SiO₂ thin films have C–H species and hydrogen content (～8 at%) at 150 °C because the cross-linking rates of SiO₂ polymerization may reduce below 200 °C. There were no significant changes in the ratio of O/Si (～2.1) according to the growth temperatures. On the other hand, the film density slightly increased from 2.0 to 2.2 although the growth rate slightly decreased after 200 °C. The breakdown strength of SiO₂ also increases from 6.20 ± 0.82 to 7.42 ± 0.81 MV/cm. These values suggest that high cross-linking rate and film density may enhance the electrical property of rapid SiO₂ ALD films at higher growth temperature.     

Effect of annealing on conversion efficiency of nanostructured CdS/CuInSe2 heterojunction thin film solar cell prepared by chemical ion exchange route at room temperature

We report, the effect of air annealing on solar conversion efficiency of chemically grown nanostructured heterojunction thin films of CdS/CuInSe₂, such 100, 200 and 300 °C air annealed thin films characterized for physicochemical and optoelectronic properties. XRD pattern obtained from annealed thin films confirms tetragonal crystal geometry of CuInSe₂ and an increase in average crystallite size from 16 to 32 nm. An EDAX spectrum confirms expected and observed elemental composition in thin films. AFM represents high energy induced grain growth and agglomeration due to polygonization process. Increase in optical absorbance strength and decrease in energy band gap from 1.36 to 1.25 eV is observed. Increase in charge carrier concentration from 2 × 10¹⁶ to 8 × 10¹⁷ cm^?3 is observed as calculated from Hall effect measurements and an enhancement in solar conversion efficiency from 0.26 to 0.47% is observed upon annealing.     

Synthesis and characteristics of nature-superlattice-structured Bi3TiNbO9–Bi4Ti3O12 ferroelectric thin films by MOD

Natural-superlattice-structured ferroelectric thin films, Bi₃TiNbO₉–Bi₄Ti₃O₁₂ (BTN–BIT), have been synthesized on Pt/Ti/SiO₂/Si by metal organic decomposition (MOD) using BTN–BIT (1 mol:1 mol) solution. BTN–BIT films show natural-superlattice peaks below 2θ = 20° in X-ray diffraction patterns, which indicate that the BTN–BIT films annealed at 700–800 °C in O₂ ambient are consisted of iteration of two unit cells of Bi₃TiNbO₉ and one unit cell of Bi₄Ti₃O₁₂. As the annealing temperature increases from 600 to 750 °C, uniform and crack-free films, better crystallinity and ferroelectric properties can be obtained, but the pyrochlore phase in BTN–BIT films annealed over 800 °C would impair the ferroelectric properties. With the increase of O₂ flow rate from 0.5 to 1.5 L/min, both remanent polarization P_r and coercive electric field E_C increase, which are mainly attributed to reduction of the vacanvies of Bi and oxide ions in the films. Natural-superlattice-structured BTN–BIT thin films having 2–1 superlattice annealed at 750 °C in O₂ ambient with a flow rate of 1.5 L/min exhibit superior ferroelectric properties of P_r = 23.5 μC/cm² and E_C = 135 kV/cm.     

Synthesis of TiO2 thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO₂ thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, {TIP, Ti(OⁱPr)₄} and Bis(dimethylamido)titanium diisopropoxide, {BTDIP, (Me₂N)₂Ti(OⁱPr)₂} were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO₂ polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO₂ thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO₂ thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO₂ film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO₂ film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO₂ film synthesized with BTDIP precursor to apply dye-sensitized solar cell.     

Isothermal oxidation behavior of the TZAV-20 alloy

Oxidation behavior is important for secure and long-life service of metals and alloys. The isothermal oxidation behavior of the Ti–20Zr–6.5Al–4V alloy at 470 to 670 °C was investigated. The kinetics analysis shows that the oxidation of TZAV-20 alloy below 570 °C accords with the parabolic law. While the alloy oxidized at 670 °C, obeys the linear law. As oxidation temperature increases from 470 to 670 °C, the oxidation products change as: TiO₂ → TiO₂ + ZrO₂ → TiO₂ + ZrO₂ + Al₂O₃. Relation between weight gain and thickness of oxidation film shows that the weight will increase 0.171 mg/cm² for every 1 μm increasing in thickness. The surface hardness increases from approximately 380 HV for base material to 689 HV for 670 °C oxidized specimen. In short, the TZAV-20 alloy has favorable inoxidizability below 570 °C. The findings will not only promote practical applications of the new TiZrAlV series alloys but also supplement the oxidation theory.     

Hardness enhancement and oxidation resistance of nanocrystalline TiN/MoxC multilayer films

In this paper the influence of the layer's microstructure on the hardness enhancement in multilayer nanocrystalline films and the oxidation resistance are studied. The TiN/Mo_xC multilayer films at different modulation period, and Mo_xC and TiN monolayer films were deposited on the (0 0 1) silicon wafers and molybdenum sheets by rf and dc magnetron sputtering. The monolayer TiN films with a thickness of about 2 μm are of pure face-center cubic TiN phase, while the monolayer Mo_xC films consist of two phases, one of which is body-center cubic Mo and the other is hexagonal Mo₂C as determined by XRD. The coarse columnar grains of about 200 nm in the monolayer TiN films become much smaller or disappear in the multilayer films. The hardness enhancement of the multilayer films takes place at the modulation period of 320 nm, which can reach to 26 GPa and is much higher than the values of Mo_xC and TiN monolayer films. This enhancement in hardness can be explained as the decrease in the size and/or disappearance of columnar grains in the TiN layer. The Young's modulus in the temperature range from 100 to 400 °C increases with decreasing modulation period. It is found that about 100 nm thick TiN films can increase largely the oxidation resistance of Mo_xC films.     

Effects of the sulfidation temperature on the structure,composition and optical properties of ZnS films prepared by sulfurizing ZnO films

Nanocrystalline ZnS films have been prepared by sulfidation of the reactive magnetron sputtered ZnO films. The structure, composition and optical properties of the sulfurized ZnO films as a function of the sulfidation temperature (T_S) have been systematically studied. It is found that at T_S ⩾ 400 °C ZnO is completely converted to ZnS with the hexagonal structure. The ZnS films have a strongly (0 0 2) preferred orientation and an optical transparency of about 80% in the visible region. In addition, at T_S < 444.6 °C (boiling point of sulfur), some residual sulfur decomposed from H₂S gas can adhere to the sulfurized film surface while at T_S = 580 °C a S/Zn ratio much higher than the ideal stoichiometric proportion of ZnS is obtained for the ZnS films. ZnS films with a minimum XRD FWHM value of 0.165° and a good S/Zn ratio of 0.99 are obtained at a temperature of 500 °C indicating the ZnS films to be suitable for use in the thin film solar cells.     

Effect of ZrO2-doping of nanosized Fe2O3/MgO system on its structural,surface and catalytic properties

Fe₂O₃/MgO system was prepared by wet impregnation method followed by treatment with different amounts of Zr-dopant salt then heating at 500 and 700 °C. The dopant concentrations were 0.48, 0.95 and 1.4 mol% ZrO₂. Pure and variously doped solids were characterized using XRD, N₂-adsorption isotherms carried out at ?196 °C and catalytic decomposition of H₂O₂ in aqueous solution at 25–35 °C. The results revealed that the nanosized MgO phase was only detected in the diffractograms of pure and doped solids calcined at 500 °C. Heating pure and doped solids at 700 °C produced nanosized MgFe₂O₄ phase together with MgO phase. Pure and ZrO₂-doped solids calcined at 500 and 700 °C are mesoporous adsorbents. The doping process brought about a measurable decrease in the S_BET of Fe₂O₃/MgO system with subsequent increase in its catalytic activity. The catalytic activity of the investigated system toward H₂O₂ decomposition, expressed as reaction rate constant per unit surface area was found to increase as a function of dopant concentration. The maximum increase in the reaction rate constant per unit surface area measured for the reaction carried out at 30 °C attained 125% for the heavily doped samples. This significant increase was based on the catalytic activity of pure catalyst sample measured under the same conditions.     

Effect of heat treatment on microstructure,hardness and rollability of V55Ti30Ni15 alloy membranes

The effect of heat treatment on the microstructure, hardness and rollability of V₅₅Ti₃₀Ni₁₅ alloy membranes has been investigated in this study. The microstructure resulting from different heat treatment conditions has a great influence on hardness. Fine NiTi particles precipitate from the supersaturated V-matrix solid solution at temperatures above 600 °C, increase in quantity until 800 °C, then dissolve back into the V-matrix with a further increase in temperature up to 950 °C. The resultant hardness decreases with temperature until 800 °C, and then increases from 800 to 950 °C. In the present study, a comparison has been made between the rollability of the as-cast and the heat treated state selected for deformation at different rolling temperatures. The percent reduction in thickness of the heat-treated alloy (800 °C/18 h) has been found to be up to 30% higher than that of the as-cast alloy, even at room temperature (cold rolling).     

Microwave dielectric properties of BaO–TeO2 binary compounds

A series of BaO–TeO₂ binary ceramic compounds were explored for microwave dielectric applications with ultra-low processing temperatures. During the calcination of mixed BaCO₃ and TeO₂ raw powders, BaTe₄O₉, BaTe₂O₆, BaTeO₃, and Ba₂TeO₅ phases were obtained through the sequential phase formations from Te-rich to Ba-rich phases at temperatures ranging from 500 to 850 °C. Sintering temperatures were as low as only 550 °C for the Te-rich phases. Barium tellurate ceramics exhibited excellent microwave dielectric properties with intermediate dielectric permittivities and high quality factors (Q). The dielectric properties at microwave frequencies were ε_r = 10–21, Q × f = 34,000–55,000 GHz, and TCf = − 51 to − 124 ppm/°C, depending on compositions.     

Effect of substrate temperature on the properties of pyrolytically deposited nitrogen-doped zinc oxide thin films

The effect of substrate temperature (T_s) on the properties of pyrolytically deposited nitrogen (N) doped zinc oxide (ZnO) thin films was investigated. The T_s was varied from 300 °C to 500 °C, with a step of 50 °C. The positive sign of Hall coefficient confirmed the p-type conductivity in the films deposited at 450 °C and 500 °C. X-ray diffraction studies confirmed the ZnO structure with a dominant peak from (1 0 0) crystal plane, irrespective of the variation in T_s. The presence of N in the ZnO structure was evidenced through X-ray photoelectron spectroscopy (XPS) analysis. The obtained high N concentration reveals that the 450 °C is the optimal T_s. Atomic force microscope (AFM) analysis showed that the surface roughness was increased with the increasing T_s until 400 °C but then decreased. It is found that the transmittance of the deposited films is increased with the increasing T_s. The optical band gap calculated from the absorption edge showed that the films deposited with T_s of 300 °C and 350 °C possess higher values than those deposited at higher T_s.     

Photovoltaic performance of dye sensitized solar cell based on rutile TiO2 scaffold electrode prepared by a 2 step bi-layer process using molten salt matrices

Dye sensitized solar cells were made on TiO₂ scaffold anodes of rutile particles. These TiO₂ scaffold anodes were grown from rutile seeds by using a molten salt synthesis technique. Different thickness coatings of mixed amorphous titanium hydroxide and NaCl–KCl eutectic salt mixture on the rutile seeds were heat treated at different temperatures. The rutile whiskers of different aspect ratios were grown depending on the growth temperature. The best photovoltaic performances were obtained for the device made from the scaffold of 20–50 nm diameter and 0.5–1 μm length nanowhiskers obtained at 700 °C for 5 h of treatment.     

Ultraviolet–green photoluminescence of β-Ga2O3 films deposited on MgAl6O10 (1 0 0) substrate

β-Ga₂O₃ films were grown on double-side polished MgAl₆O₁₀ (1 0 0) substrate by metal organic chemical vapor deposition (MOCVD) at 600, 650 and 700 °C. The refractive index dispersive behaviors of Ga₂O₃ films have the typical shape of the normal dispersion curve. Photoluminescence (PL) spectra measured at room temperature revealed that all the films exhibited intense ultraviolet (UV)–green emission from 300 to 650 nm. A minor deep UV emission around 275 nm (∼4.51 eV) was observed for the sample prepared at 700 °C. The intensity of the emission increased markedly when measured at low temperature. The corresponding PL mechanisms were discussed in detail and a schematic diagram was proposed.     

Cordierite as catalyst support for nanocrystalline CuO/Fe2O3 system

CuO, Fe₂O₃ and CuO–Fe₂O₃ samples supported on cordierite (commercial grade) were prepared by wet impregnation method using finely powdered support material, copper and/or iron nitrates. The extent of loading was varied between 5 and 20 wt.% CuO, Fe₂O₃ or CuO–Fe₂O₃. The physicochemical, surface and catalytic properties of the various solids calcined at 350–700 °C were investigated using XRD, EDX, nitrogen adsorption at 77 K and CO-oxidation by O₂ at 220–280 °C.The results obtained revealed that the employed cordierite preheated at 350–700 °C was well-crystallized magnesium aluminum silicate (Mg₂Al₄Si₅O₁₈). Loading of 20 wt.% CuO or Fe₂O₃ on the cordierite surface calcined at 350 °C led to a partial dissolution of the added oxides in the support lattice forming solid solutions. The other portions remained as separate nanocrystalline CuO or Fe₂O₃ phases. The dissolved portions of the transition metal oxide increased upon increasing the calcination temperature from 350 to 500 °C. Loading of 20 wt.% CuO–Fe₂O₃ on the cordierite surface followed by calcination at 350 °C resulted in a solid–solid interaction between some of CuO and Fe₂O₃ yielding iron cuprate Fe₂CuO₄, which decomposed at ≥500 °C yielding copper and iron oxides. The portion of Fe₂O₃ dissolved in the cordierite lattice at 500 °C is twice that of CuO.The S_BET of cordierite increased several times by treating with small amounts of Fe₂O₃ or CuO. The increase was more pronounced by treating with Fe₂O₃. The catalytic activity of the cordierite increased progressively by increasing the amount of oxide(s) added. The mixed oxides system supported on cordierite and calcined at 350–700 °C showed catalytic activities much bigger than those measured for the individual supported systems. The synergistic effect manifested in case of solids calcined at 350 °C was attributed to the formation of surface iron cuprate. The significant increase in surface concentration of copper species on top surface layers of the solids treated with mixtures of copper and ferric oxides could be responsible for the synergistic effect for the mixed oxide catalysts calcined at 500 or 700 °C.     

Oxidation behavior of amorphous metallic Ni3(SbTe3)2 compound

Amorphous Ni₃(SbTe₃)₂ compound was prepared from a metathesis between Zintl phase K₃SbTe₃ and NiBr₂ in solution and its oxidation behavior was investigated in the temperature range of 200–700 °C in air. To characterize the sample, thermogravimetry (TG), X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive analysis by X-ray (EDAX) analyses were performed and electrical conductivity was measured as a function of temperature in the range of 25–800 °C in air. The specimen showed a metallic conducting-like behavior below 585 °C while a semiconducting-like behavior above 585 °C. At a first oxidation step of Ni₃(SbTe₃)₂ below 500 °C, TeO₂ phase is formed. Above 500 °C, NiO phase is formed, then some NiO reacts with TeO₂ to form NiTeO₃ and NiSb₂O₆ is simultaneously formed. Above 700 °C, NiTeO₃ is further reacted with TeO₂ to form NiTe₂O₅. Both NiTeO₃ and NiTe₂O₅ are decomposed above 774 °C.     

Crystallization of nanosized Aurivillius phase Bi2W2O9 from amorphous precursor

Nanoparticles of bismuth layered Aurivillius phase, Bi₂W₂O₉, have been synthesized by annealing of precursor prepared by high energy milling in ball mill. The obtained powders have been investigated using the XRD, TEM, SEM, diffuse reflectivity, Raman and infrared spectroscopy. The results show that mechanochemical activation allows obtaining Bi₂W₂O₉ at much lower temperatures than those required in a conventional solid state reaction or synthesis through a complex organic precursor. As a result, material with smaller grain size can be obtained. Therefore this synthesis method is the best route to enhance photocatalytic activity of Bi₂W₂O₉. Our results also show that milling time has great impact on the crystallization mechanism. Bi₂W₂O₉ crystallizes easily already at 600 °C from precursor milled by 8 h. However, prolong milling time results in stabilization of an unknown phase or phases, which crystallize below 700 °C, and transform into the well-known Bi₂W₂O₉ phase after annealing at 750 °C.     

Annealing effect on the microstructure and photoluminescence of ZnO thin films

Zinc oxide thin films have been obtained by pulsed laser ablation of a ZnO target in O₂ ambient at a pressure of 0.13 Pa using a pulsed Nd:YAG laser. ZnO thin films deposited on Si (1 1 1) substrates were treated at annealing temperatures from 400 °C up to 800 °C after deposition. The structural and optical properties of deposited thin films have been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, photoluminescence spectra, resistivity and IR absorption spectra. The results show that the obtained thin films possess good single crystalline with hexagonal structure at annealing temperature 600 °C. Two emission peaks have been observed in photoluminescence spectra. As the post-annealing temperature increase, the UV emission peaks at 368 nm is improved and the intensity of blue emission at 462 nm decreases, which corresponds to the increasing of the optical quality of ZnO film and the decreasing of Zn interstitial defect, respectively. The best optical quality for ZnO thin films emerge at post-annealing temperature 600 °C in our experiment. The measurement of resistivity also proves the decrease of defects of ZnO films. The IR absorption spectra of sample show the typical Zn–O bond bending vibration absorption at wavenumber 418 cm⁻¹.     

CuAlxGa1−xSe2 thin films for photovoltaic applications: Structural,electrical and morphological analysis

Wide-bandgap quaternary semiconductor chalcopyrites can be of interest for photovoltaic application. Novel CuAl_xGa_1?xSe₂ (CAGS) (0 ≤ x ≤ 1) thin films have been achieved by selenization of evaporated metallic precursor layers in a wide range of Al content and for several film thicknesses. Influence of Al incorporation, x, and film thickness on the structural, electrical and morphological properties of the samples have been studied. Polycrystalline CAGS thin films have been obtained reproducibly with chalcopyrite structure. The lattice parameters, a and c, and the average crystallite size decreased with the increase of Al amount, x. All films showed random orientation with the degree of randomness reduced for increasing x values. All samples show photoconductivity and resistivities ranging from 10¹ to 10⁴ Ω cm depending on the film thickness and x value. Resistivity values increase and thermoelectric coefficient decreases with the increase of Al proportion, x. Surface morphology was studied by SEM images and roughness measurements. Grain size and the arithmetic average roughness decreases with the increase of x and with the decrease of film thickness.