Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

Pulsed laser deposition of anatase and rutile TiO2 thin films

The investigation deals with the preparation of both anatase and rutile thin films from a sintered rutile target of TiO₂ by pulsed laser ablation technique. Microstructural characterization of the sintered target was carried out using X-ray diffraction and AC impedance spectroscopy. Thin films of titania were deposited on (111) Si substrates at 673 K in the laser energy range 200-600 mJ/pulse at two different conditions: (i) deposition at 3.5 × 10^− 5 mbar of oxygen, and (ii) deposition at an oxygen partial pressure of 0.1 mbar. The influence of laser energy and oxygen addition on the film growth has been studied. X-ray diffraction analysis of the films indicated that the films are single phasic and nano crystalline. Titania films deposited in the energy range 200-600 mJ/pulse at a base pressure of 5 × 10^− 5 mbar are rutile with particle sizes in the range 5-10 nm, whereas the films formed at the oxygen partial pressure 0.1 mbar are anatase with particle sizes in the range 10-24 nm. In addition, at higher energies, a significant amount of particulates of titania are found on the surface of the films. The change in the microstructural features of the films as a function of laser energy and oxygen addition is discussed in relation with the interaction of the ablated species with the background gas.     

Structural and dielectric properties of Bi2Zn2/3Nb4/3O7 thin films prepared by pulsed laser deposition at low temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited on Pt/TiO₂/SiO₂/Si(1 0 0) substrates at a room temperature under the oxygen pressure of 1-10 Pa by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were then post-annealed below 200 °C in a rapid thermal process furnace in air for 20 min. The dielectric and leakage current properties of Bi₂Zn_2/3Nb_4/3O₇ thin films are strongly influenced by the oxygen pressure during deposition and the post-annealing temperature. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited under 1 Pa oxygen pressure and then post-annealed at a temperature of 150 °C show uniform surface morphologies. Dielectric constant and loss tangent are 57 and 0.005 at 10 kHz, respectively. The high resolution TEM image and the electron diffraction pattern show that nano crystallites exist in the amorphous thin film, which may be the origin of high dielectric constant in the Bi₂Zn_2/3Nb_4/3O₇ thin films deposited at low temperatures. Moreover, Bi₂Zn_2/3Nb_4/3O₇ thin film exhibits the excellent leakage current characteristics with a high breakdown strength and the leakage current density is approximately 1 × 10⁻⁷ A/cm² at an applied bias field of 300 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films are potential materials for embedded capacitor applications.     

Low temperature growth of rutile TiO2 films in modified rf magnetron sputtering

Low temperature (≤300°C) growth of rutile TiO₂ films with high refractive index which is equal to bulk TiO₂ crystal was achieved by using a modified sputtering method. Depositions were carried out in rf magnetron sputtering apparatus equipped with an auxiliary permanent magnet just under the grounded electrode. The as-deposited films showed rutile polycrystalline structure and fine surface morphology indicating higher densification. Remarkable changes in composition, total current and energy of incident ions were presented at a Ar–O₂ total pressure of 2.7 Pa. The rutile phase grows in a modified sputtering method in contrast with anatase phase growth in conventional sputtering apparatus.     

Low temperature growth of nanocrystalline TiO2 films with Ar/O2 low-field helicon plasma

TiO₂ thin films were deposited on silicon wafer substrates by low-field (1 < B < 5 mT) helicon plasma assisted reactive sputtering in a mixture of pure argon and oxygen. The influence of the positive ion density on the substrate and the post-annealing treatment on the films density, refractive index, chemical composition and crystalline structure was analysed by reflectometry, Rutherford backscattering spectroscopy (RBS) and X-ray diffraction (XRD). Amorphous TiO₂ was obtained for ion density on the substrate below 7 × 10¹⁶ m^− 3. Increasing the ion density over 7 × 10¹⁶ m^− 3 led to the formation of nanocrystalline (~ 15 nm) rutile phase TiO₂. The post-annealing treatment of the films in air at 300 °C induced the complete crystallisation of the amorphous films to nanocrystals of anatase (~ 40 nm) while the rutile films shows no significant change meaning that they were already fully crystallised by the plasma process. All these results show an efficient process by low-field helicon plasma sputtering process to fabricate stoichiometric TiO₂ thin films with amorphous or nanocrystalline rutile structure directly from low temperature plasma processing conditions and nanocrystalline anatase structure with a moderate annealing treatment.     

Electrical and optical properties of tantalum oxide thin films prepared by reactive magnetron sputtering

Tantalum oxide thin films were prepared by using reactive dc magnetron sputtering in the mixed atmosphere of Ar and O₂ with various flow ratios. The structure and O/Ta atom ratio of the thin films were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The optical and dielectric properties of the Ta₂O₅ thin films were investigated by using ultraviolet-visible spectra, spectral ellipsometry and dielectric spectra. The results reveal that the structure of the samples changes from the amorphous phase to the β-Ta₂O₅ phase after annealing at 900 °C. The XPS analysis showed that the atomic ratio of O and Ta atom is a stoichiometric ratio of 2.50 for the sample deposited at Ar:O₂ = 4:1. The refractive index of the thin films is 2.11 within the wavelength range 300-1000 nm. The dielectric constants and loss tangents of the Ta₂O₅ thin films decrease with the increase of measurement frequency. The leakage current density of the Ta₂O₅ thin films decreases and the breakdown strength increases with the increase of Ar:O₂ flow ratios during deposition.     

Effect of Nb doping on the phase transition and optical properties of sol-gel TiO2 thin films

Various content Nb-doped TiO₂ thin films were prepared by sol-gel process. XRD analysis shows that the existence of crystalline TiO₂ in anatase and rutile form depends on the Nb content in the examined samples. It is observed that Nb promotes the anatase to rutile phase transition but has a depression effect on the anatase grain growth. It is found that incorporation of about 4 at.% of Nb completely transforms anatase TiO₂ to the rutile form at a calcination temperature as high as 900 °C. The mechanism is proposed. Optical analyses show that the films have an average of 60% transmission in visible region. The energy gap values using Tauc's formula have also been estimated. The band gap of rutile Ti_1−xNb_xO₂ solid solutions increases with increasing x.     

Fabricating TiO2 Photocatalysts by rf Reactive Magnetron Sputtering at Varied Oxygen Partial Pressures

Titanium dioxide (TiO₂) thin films were fabricated onto non-alkali glass substrates by rf reactive magnetron sputtering at room temperature using Ti-metal target at varied oxygen partial pressure [O₂/(Ar + O₂)]. The sputtering deposition was performed under an rf power of 200 W. The target to substrate distance was kept at 80 mm, and the total gas pressure was 10 mTorr after 2 h of deposition. It was found that the crystalline structure, surface morphology, and photocatalytic activities of the TiO₂ thin films were affected by the oxygen partial pressure during deposition. The XRD patterns exhibited a broad-hump shape indicating the amorphous structure of TiO₂ thin films. The thin films deposited at a relatively high value of oxygen partial pressure (70%) had a good photo-induced decomposition of methylene blue (MB), photo-induced hydrophilicity, and had a small grain size.     

Study of bactericidal efficiency of magnetron sputtered TiO2 films deposited at varying oxygen partial pressure

TiO₂ thin films have been deposited at different Ar:O₂ gas ratios (20:80,70:30,50:50,and 40:60 in sccm) by rf reactive magnetron sputtering at a constant power of 200 W. The formation of TiO₂ was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen percentage in the films was found to increase with an increase in oxygen partial pressure during deposition. The oxygen content in the film was estimated from XPS measurement. Band gap of the films was calculated from the UV-Visible transmittance spectra. Increase in oxygen content in the films showed substantial increase in optical band gap from 2.8 eV to 3.78 eV. The Ar:O₂ gas ratio was found to affect the particle size of the films determined by a transmission electron microscope (TEM). The particle size was found to be varying between 10 and 25 nm. The bactericidal efficiency of the deposited films was investigated using Escherichia coli (E. coli) cells under 1 h UV irradiation. The growth of E. coli cells was estimated through the Optical Density measurement by UV-Visible absorbance spectra. The qualitative analysis of the bactericidal efficiency of the deposited films after UV irradiation was observed through SEM. A correlation between the optical band gap, particle size and bactericidal efficiency of the TiO₂ films at different argon:oxygen gas ratio has been studied.     

Properties of TiO2 film prepared from titanium tetrachloride

The properties of TiO₂ film prepared by titanium tetrachloride were investigated with respect to annealing temperatures in terms of phase change, crystallite size, and band gap energy. The TiO₂ film dried at room temperature exhibited an amorphous phase, while films calcined above 281 and at 990°C displayed anatase TiO₂ and a mixture of anatase and rutile, respectively. The TiO₂ film was transformed to an anatase phase through three stages during the annealing processes: (1) removal of water, (2) decomposition of a peroxo group, and (3) amorphous-anatase phase transformation. It was also found that the bandgap energy of TiO₂ film was changed with increasing annealing temperature. This is attributed to the quantum size effect in the range of 475–675°C and to the formation of rutile phase having lower band gap energy than anatase in the range of 675–990°C.     

Elaboration and characterization of nanocrystalline TiO2 thin films prepared by sol–gel dip-coating

Nanocrystalline TiO₂ thin films were deposited on a ITO coated glass substrate by sol–gel dip coating technique, the layers undergo a heat treatment at temperatures varying from 300 to 450 °C. The structural, morphological and optical characterizations of the as deposited and annealed films were carried out using X-ray diffraction (XRD), Raman spectroscopy, Atomic Force Microscopy (AFM), visible, (Fourier-Transform) infrared and ultraviolet spectroscopy, Fluorescence and spectroscopic ellipsometry. The results indicate that an anatase phase structure TiO₂ thin film with nanocrystallite size of about 15 nm can be obtained at the heat treatment temperature of 350 °C or above, that is to say, at the heat treatment temperature below 300 °C, the thin films grow in amorphous phase; while the heat treatment temperature is increased up to 400 °C or above, the thin film develops a crystalline phase corresponding to the titanium oxide anatase phase. We have accurately determined the layer thickness, refractive index and extinction coefficient of the TiO₂ thin films by the ellipsometric analysis. The optical gap decreases from 3.9 to 3.5 eV when the annealing temperature increases. Photocatalytic activity of the TiO₂ films was studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that films annealed above 350 °C had good photocatalytic activity which is explained as due to the structural and morphological properties of the films.     

Defect evolution of nanocrystalline SnO2 thin films induced by pulsed delivery during in situ annealing

The microstructural defects of nanocrystalline SnO₂ thin films prepared by pulsed laser deposition have been investigated using transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy. Defects inside nanocrystalline SnO₂ thin films could be significantly reduced by in situ annealing SnO₂ thin films at 300 °C for 2 h. High-resolution transmission electron microscopy showed that the stacking faults and twins were annihilated upon in situ annealing. In particular, the inside of the SnO₂ nanoparticles demonstrated perfect lattices free of defects after in situ annealing. Raman spectra also confirmed that the in situ annealed specimen was almost defect-free. By using in situ annealing, defect-free nanocrystalline SnO₂ thin films can be prepared in a simple and practical way, which holds the promise for applications as transparent electrodes and solid-state gas sensors.     

Dielectric properties of Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> thin films deposited onto Ti and TiO<Subscript>2</Subscript> layer

The present study describes the dielectric properties of RF sputtered Ta₂O₅ thin films as a function of the buffer layer and annealing condition. The buffer layers were Ti or TiO₂. And the thin film was annealed in various conditions. The X-ray pattern results showed that the phase of the RF sputtered Ta₂O₅ thin films was amorphous and this state was kept stable to RTA (rapid thermal annealing) even at 700°C. Measurements of the electrical and dielectric properties of the reactive sputtered Ta₂O₅ fabricated in two simple metal insulator semiconductor (MIS) structures, (Cu/Ta₂O₅/Ti/Si/Cu and Cu/Ta₂O₅/TiO₂/Si/Cu) indicated that the amorphous Ta₂O₅ grown on Ti possesses a high dielectric constant (30–70) and high leakage current (10⁻¹–10⁻⁴ A/cm²), whereas a relatively low dielectric constant (−10) and low leakage current (−10⁻¹⁰ A/cm²) were observed in the amorphous Ta₂O₅ deposited on the TiO₂ buffer layer. In addition, the leakage current mechanisms of the two amorphous Ta₂O₅ thin films were investigated by plotting the relation of current density (J) vs. applied electric field (E). The Ta₂O₅/Ti film exhibited three dominant conduction mechanism regimes contributed by the Ohmic emission at low electrical field, by the Schottky emission at intermediate field and by the Poole-Frenkel emission at high field. In the case of Ta₂O₅/TiO₂ film, the two conduction mechanisms, the Ohmic and Schottky emissions, governed the leakage current density behavior. The conduction mechanisms at various electric fields applied were related to the diffusion of Ta, Ti and O, followed by the creation of vacancies, in the rapid thermal treated capacitors.     

Synthesis and characterization of hardness-enhanced multilayer oxide films for high-temperature applications

Multilayer oxide coatings consisting of amorphous Al₂O₃ and crystalline TiO₂ nanolayers have been deposited using reactive pulsed d.c. magnetron sputtering at different partial pressures of oxygen. Hardness enhancement has been observed in oxide multilayer coatings with amorphous Al₂O₃ as the majority component. These coatings had greater hardness-to-modulus ratios and showed greater resistance to wear over monolithic Al₂O₃ and TiO₂ majority phase multilayers. Multilayer films retain their high hardness up to ~ 800 °C in air; some hardness enhancement in the Al₂O₃ majority phase multilayer coating remains even after 1 h of air annealing at 1000 °C. The hardness decrease at elevated temperatures is due to the roughening of interfaces between nanolayers, which can be attributed to the annealing-driven change of crystallographic texture of TiO₂ layers.     

Synthesis and characterization of Cu2ZnSnS4 thin films grown by PLD: Solar cells

As-deposited and annealed Cu₂ZnSnS₄ (CZTS) thin films have been synthesized onto Mo coated glass substrates at different deposition times using pulsed laser deposition (PLD) technique. The effect of deposition time (film thickness) and annealing onto the structural, morphological, compositional and optical properties of CZTS thin films have been investigated. The polycrystalline CZTS thin films with tetragonal crystal structure have been observed from structural analysis. FESEM and AFM images show the smooth, uniform, homogeneous and densely packed grains and increase in the grain size after annealing. The internal quantitative analysis has been carried out by XPS study which confirms the stoichiometry of the films. The optical band gap of CZTS films grown by PLD is about 1.54 eV, which suggests that CZTS films can be useful as an absorber layer in thin film solar cells. Device performance for deposited CZTS films has been studied.     

Effect of Na diffusion from glass substrate on the microstructural and photocatalytic properties of post-annealed TiO2 films synthesised by reactive sputtering

Amorphous columnar TiO₂ films were synthesised by reactive sputtering on cold soda–lime glass substrates (TiO₂/glass films). The films were subsequently heated in order to crystallise the photoactive anatase phase. The surface chemical composition assessment demonstrates the occurrence of metallic Na, the amount of which increases with the annealing temperature. The evolution of the structural, microstructural and photocatalytic properties of the films with the annealing temperature was investigated and compared to that of TiO₂ films deposited in same conditions, but on glass pre-coated with a SiN_x diffusion barrier (TiO₂/SiN_x/glass films). Once crystallised, both series of TiO₂ films exhibit [001] preferential orientation corresponding to the columnar growth. Grain coalescence associated to a modification of the grain shape is only observed in TiO₂/glass films for annealing temperatures higher than 450 °C, whereas neither microstructural nor structural change is observed in TiO₂/SiN_x/glass films. The Na-contaminated TiO₂ films exhibit different photocatalytic behaviour with the annealing temperature compared to the Na-free TiO₂ films. A discussion is finally based on these differences.     

Structural characteristics and resistive switching properties of thermally prepared TiO2 thin films

Polycrystalline TiO₂ thin films were formed on Pt(1 1 1)/Ti/SiO₂/Si by thermal oxidation of Ti films with temperatures ranging from 600 °C to 800 °C. Results of Raman spectra testing indicate that the structure of the oxidized TiO₂ films is rutile phase. The resistance switching behaviors (RSB) have been confirmed in Pt/TiO₂/Pt structures. A stable RSB with a narrow dispersion of the resistance states and switching voltages was observed in the sample fabricated with the oxidation temperature of 600 °C. The resistance ratios of high resistance states to low resistance states are larger than 10³ with the set and reset voltage as low as 2.5 V and 0.6 V, respectively.     

Structural and photoelectrochemical properties of Ti1−xWxO2 thin films deposited by magnetron sputtering

W-doped titanium dioxide is a promising candidate material for applications ranging from UV–VIS light photocatalytic reactions to catalyst support in proton-exchange membrane fuel cells, depending on the doping content. The present study reports on the possibility to synthesize substitutional Ti_1?xW_xO₂ thin films with 0 ≤ x ≤ 1 by magnetron co-sputtering from Ti and W metallic targets. Two routes were investigated starting from 1) crystalline titanium tungsten alloys deposited in non-reactive (pure Ar) mode, and 2) amorphous titanium tungsten oxides deposited in reactive (Ar + O₂ atmosphere) mode. The structure and phase stability after air annealing at 550 °C has been investigated by X-ray Diffraction (XRD). X-ray Reflectivity (XRR) was used to determine the change in film mass density upon annealing. Films of the non-reactive mode series could not be successfully fully oxidized into Ti_1?xW_xO₂ form. For the reactive mode film series, ternary Ti_1?xW_xO₂ oxides were obtained after air annealing and the crystal structure was changed from anatase to rutile with increasing W content in the range 0–33 at.%. Films with higher W content (0.33< x ≤ 1) eventually crystallized in the WO₃ triclinic structure. Photo-electrodes were elaborated from the deposited thin films on FTO coated glass, and they all showed photo-response when tested in acid solution, under UV–VIS illumination. Among the doped materials, the Ti_0.92W_0.08O₂ thin film showed the highest photo-current.     

Deposition of PZT thin film onto copper-coated polymer films by mean of pulsed-DC and RF-reactive sputtering

In this work, Pb(Zr,Ti)O₃ (PZT) thin films were deposited onto flexible Cu-coated Kapton® substrates by means of reactive magnetron sputtering for the first time. Different power supplies were selected for each of the 200 mm targets to adjust film composition and substrate ion bombardment. High-power pulse sputtering has been employed for the Zr-target to enhance for formation of nanocrystals, pulsed DC sputtering for the Ti-target to provide a high enough sputter yield, and RF-sputtering for the Pb-target to prevent droplet formation. The deposited films had a lead-enriched layer at the surface and their film composition was in rhombohedral range near the morphotropic phase boundary of the PZT phase diagram. XRD revealed a nanocrystallite mixture of lead, zirconium and titanium oxides in the as-deposited films which can be transferred into perovskite Pb(Zr,Ti)O₃ by rapid temperature annealing. Observed piezoelectric properties demonstrate that rapid-temperature-annealed films are promising for application in flexible piezoelectric sensors, actuators and power generators.     

Thin nanocrystalline TiO2–SnO2 sprayed films: Influence of the dopant concentration,substrate and thermal treatment on the phase composition and crystallites sizes

Thin nanocrystalline TiO₂–SnO₂ films (0–50 mol% SnO₂) are coated on quartz and stainless steel substrates by spray pyrolysis method. The synthesized films are investigated by XRD, Raman spectroscopy and XPS.The diffraction peaks of anatase phase fade while the peaks of rutile phase appear in the X-ray profiles with increasing of the treatment temperature and the content of SnO₂ in the sprayed films. It is found that SiO₂ coming from the quartz substrate stabilizes the anatase phase up to 700 °C. A more pronounced crystallization of rutile is registered with the films deposited on stainless steel substrate, which probably is caused by combined effect of SnO₂ doping and penetration of iron and chromium from the substrate inside the films.Dopant concentration (SnO₂) influences the size of the crystallites of the titania films deposited on quartz substrates The size of crystallites in the titania films decreases from 45 to 25 nm with increasing of SnO₂ amount.The SnO₂ amount does not affects substantially the size of crystallites (about 23 nm) for the films deposited on stainless steel.